Polymer Testing 68 (2018) 135–145

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Polymer Testing
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Rigid polyurethane foams reinforced with industrial potato protein T

a,∗ b a
Sylwia Członka , Massimo F. Bertino , Krzysztof Strzelec
a
Institute of Polymer & Dye Technology, Lodz University of Technology, Lodz, Poland
b
Department of Physics, Virginia Commonwealth University, Richmond, VA, USA

A R T I C LE I N FO A B S T R A C T

Keywords: Potato protein (PP), the main product of thermal and acidic coagulation of potato juice obtained from potatoes
Polyurethane during starch production, was selected as a reinforcement filler in polyurethane (PU) foams. Rigid polyurethane
Rigid polyurethane foam foams (RPUFs) were successfully obtained from a two-component system and modified with PP, in the range of
Cellular structure 0.1–5 wt% of total polymer mass content. The influence of PP on the RPUFs morphology and on physical and
Filler
mechanical properties of the obtained porous materials were studied. PU foams were characterized using
Potato protein
morphological, mechanical and thermal analysis. The results show that an addition of 0.1 wt% PP improves
compressive strength (the final strength up to 230 kPa) due to the strengthening effect of the filler, low thermal
conductivity (0.029 W/m·K) and low water absorption (14.3%). The results obtained in this study confirm that
the addition of PP over a certain optimal level has a negative effect on the cell morphology, leading to a de-
terioration of the physico-mechanical properties of the modified foams.

1. Introduction sources has been observed.

Polyurethanes (PUs) are polymers with a wide range of applications
that can display quite different properties according to the chemical
reagents used in their synthesis. One of the most important commercial
applications of made of PU materials is rigid polyurethane foams
(RPUFs) [1]. A common approach for making PU foams is by reaction of
a polyol and an isocyanate, which forms the backbone urethane group.
Typically, a blowing agent is used to create cells within the foam. Ad-
ditional modulating agents, such as, catalysts and surfactants, can be
added during production to modulate the properties of the resulting
foam [2].
PU foams have rapidly grown to be one of the most diverse and
widely used plastics with a continuously increasing global market [3].
RPUFs are commonly used in a variety of industries including auto-
motive, furniture, construction, packaging and manufacturing [4]. In
buildings, they are usually employed as insulating materials for pipe-
lines and lightweight construction components e.g. parts of door and
window frames, furniture or home and commercial refrigeration
equipment [5].
Because of the large market and numerous applications, the interest
in PUs has increased. Manufactures of PU are looking for new methods
for their modification, which would be advantageous from an economic
and ecological point of view. A question related to the production of
RPUFs is the environmental impact. In this regard, a growing tendency
to modify RPUFs with additives obtained from renewable, bio-based
A promising solution to improve the properties of obtained mate-
rials, reduce demand for non-renewable petrochemicals and limit the
emission of carbon dioxide is incorporation of natural fillers into PU
foams. Natural fillers can increase biodegradation efficiency and also
reduce cost. In addition, natural fillers improve the mechanical and
thermal properties of RPUFs. Their effectiveness as a reinforcing filler is
dependent on the method of incorporation [6], compatibility with the
component [7–9], quality of the dispersion [9–11] and loading.
Several studies have reported the results of foams reinforced with a
different types of fillers. Prociak et al. [14] synthesized polyurethane-
polyisocyanurate foams based on rapeseed oil and modified with
carbon fiber. With increasing carbon fiber content, RPUFs have a re-
duced heat rate release, reduced flammability and greater thermal
stability. Zhou et al. [11] have reported the synthesis of a series of semi-
rigid biopolyurethane foams based on palm-oil polyol and reinforced
with cellulose nanocrystals. Foams with an apparent density of 50 kg/
m3 and an improved compressive strength (up to 117 kPa) were ob-
tained. Compared to neat foam, modified compositions were char-
acterized by superior dimensional stability in freezing and heating
conditions and greater water uptake. RPUFs reinforced with wheat
straw lignin in the amount of 0–6.3 wt% of the total foam mass were
prepared by Paberza et al. [12]. RPUFs with an apparent density in the
range of 45–60 kg/m3 were obtained. It was noticed that increasing
concentration of lignin in RPUFs improved thermal insulation proper-
ties. The maximum value of compressive strength (0.35 MPa parallel to

∗
Corresponding author.
E-mail addresses: sylwia.czlonka@edu.p.lodz.pl, sczlonka@vcu.edu (S. Członka).

https://doi.org/10.1016/j.polymertesting.2018.04.006
Received 3 January 2018; Received in revised form 26 February 2018; Accepted 7 April 2018
Available online 09 April 2018
0142-9418/ © 2018 Elsevier Ltd. All rights reserved.
S. Członka et al.
the foaming direction) was reached for the foam with 1.2 wt% of lignin.
Potato is the fourth most important food crop in the world, after
rice, wheat and corn [13]. Apart from being eaten directly, a large
amount of potato is used to produce potato starch (PS) [14]. The PS
industry releases large quantities of by-product, known as potato fruit
juice (PFJ) [14]. It was reported that PFJ contains 2–5 wt% of dry
matter, of which one third is potato protein (PP) [14,15]. However, at
present, most PS processing factories discharge PFJ directly, causing
environmental pollution and resource waste, which seriously restricts
the development of the potato processing industry [14]. PP has often
been overlooked but their removal from the starch industry byproduct
is necessary to help overcome the economic impact coupled to its high
polluting capacity. Because of this, the problem of utilization of PP is
still not fully resolved and requires search for new opportunities and
technologies of its use. Addition of PP as a filler in polymer composites
seems to be a logical approach to reduce the amount of waste PP and an
obvious methodology to increase the green material in polymeric ma-
terials.
Not surprisingly, the structure and properties of protein-based bio-
polymers are being actively investigated [16–21]. For example, bio-
polymers with PP and glycerol as a plasticizer have been successfully
prepared by Du et al. [22]. The resulting materials had tensile strength
in the range of 20–25 MPa, depending on plasticizer concentration.
Molecular weight and protein structure also strongly affected the me-
chanical properties. Comparable results were also obtained by Newson
et al. [23] who examined the suitability of commercial PP for bio-based
films. Bio-films with tensile strength up to 20 MPa were obtained. The
shape of the tensile stress–strain curve in thermoformed potato-based
films was controlled by glycerol level and was independent of proces-
sing temperature. Tensile testing revealed that elongation at break in-
creased with processing temperature while Young's modulus was un-
affected by processing temperature.
Despite the use of PP in different polymer composites PP has not
been considered before as a possible filler for RPUFs. In this work, we
investigate the use of PP as a filler improve mechanical, thermal and
physical properties of RPUFs. The main goal of the present work is to
optimize the foam formulation, including PP as a filler in the reaction
mixture as well as appropriate synchronization of the amount of filler
with the reaction temperature and viscosity of reaction mixture. These
are key aspects of the blowing process, leading to obtaining products
with desirable properties. This modification can result in significant
benefits, not only from the application but also economic and ecological
point of view.
2. Material and methods
2.1. Raw materials
RPUFs were synthesized from a two-component system (Izopianol
30/10/C and Purocyn B) supplied by Purinova Sp. z o.o. Izopianol 30/
10/C used in the reaction is a fully formulated mixture containing the
mixture of polyester polyol (hydroxyl number ca. 230–250 mgKOH/g
and functionality of 2), catalyst (N,N-Dimethylcyclohexylamine), flame
retardant (Tris(2-chloro-1-methylethyl)phosphate) and chain extender
(1,2-propanediol). Purocyn B is a polymeric diphenylmethane-4,4′-dii-
socyanate (pMDI) containing 31 wt% of free isocyanate groups. Potato
136
Polymer Testing 68 (2018) 135–145
Fig. 1. PP observed in magnification of a)
×50 b) ×250 and c) the end-products
containing 0.1, 1 and 5 wt% of PP (from the
left, respectively).
protein (producer: PEPEES S.A., Łomża, Polska) was used as a biode-
gradable filler (Fig. 1a,b). According to the supplier, the potato protein
is composed of dry matter (80–85 wt%), ashes (below 4.5 wt%) and
moisture (below 11 wt%). Before adding to the polyol, the filler was
dried to a constant weight at a temperature of 70 °C and subjected to
multistage disintegration by passing through a sieve with a square mesh
size of 0.2 mm.
2.2. Preparation of RPUFs
RPUFs were produced by a single step method from a two-compo-
nent (A and B) system. Following to the information provided by the
supplier the ingredients were mixed in a ratio 100:160 (ratio of
Izopianol 30/10/C to Purocyn B). RPUFs were prepared by chemical
foaming with CO2 as the foaming agent produced by water and iso-
cyanate reaction. Composite samples were prepared with 0.1, 1 or 5 wt
% of PP (Fig. 1c). Unmodified RPUF was used as a reference. The raw
materials and formulations used in the synthesis of RPUFs are presented
in Table 1.
First, Izopianol 30/10/C was weighed out in the required propor-
tions and placed in a 1000 ml polypropylene beakers. PP was then
added and the mixture (component A) was homogenized with an
overhead stirrer at 600 rpm under ambient conditions for approxi-
mately 30 s. Next, Purocyn B (component B) was added to component A
and the mixture was stirred for 10 s at a speed rate of 1800 rpm. The
mixture was then poured into an open mould and allowed to expand
freely in the vertical direction. Obtained RPUFs were conditioned at
room temperature for 24 h. After this time, samples were cut with a
band saw into appropriate shapes (determined by testing standards)
and their physico-mechanical properties were investigated.
2.3. Characterization methods
The average size of PP was measured using a Zetasizer NanoS90
instrument (Malvern Instruments Ltd, UK). The size of particles in water
and polyol dispersion (0.04 g/l) was determined with dynamic light
scattering (DLS).
The oil absorption parameter (DBPA) of the filler was determined
according to ASTM D2414 [24] using Absorptometer C (Brabender
GmbH & Co KG, Germany). Dibutyl phthalate (DBP) was added with a
titration rate of 4.0 ml/min to 20 g of powder filler. The oil absorption
parameter was recorded and determined as DBP measured volume per
gram of analyzed sample.
The absolute viscosities of polyol and isocyanate were determined
corresponding to ASTM D2930 [25], equivalent to ISO 2555 [26], using
Table 1
Foam formulations.
Foam symbol Mass content [by weight]
Izopianol 30/10/C Purocyn B Potato protein
FR 100 160 0
FP0.1 100 160 0.1
FP1 100 160 1
FP5 100 160 5
S. Członka et al.
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 apparent density of foams was determined accordingly to ASTM
D1622 [27], equivalent to ISO 845 [28]. The densities of 5 specimens
per sample were measured and averaged.
The morphology and cell size distributions of RPUFs were examined
from the cellular structure images of foam cross-sections, which were
taken using an optical stereomicroscope Leica MZ6 (Leica
Microsystems, Germany) at 250 times magnification. All the RPUFs
were scanned in the free-rising direction. The average pore diameters
and pore size distribution were calculated using ImageJ software
(Media Cybernetics Inc.).
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). Reported spectra re-
present an average of 64 individual scans.
Thermal properties were evaluated by thermogravimetric analysis
(TGA) performed using a 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 K min−1 up to 600 °C. The
initial decomposition temperatures, T10%, T50% and T80% of mass loss
were determined.
The compressive strength of foams was determined according to
ASTM D1621 [29], equivalent to ISO 844 [30], using a Zwick Z100
Testing Machine (Zwick/Roell Group, Germany) with a load cell of 2 kN
and a speed of 2 mm/min. Samples of specified sizes (10 × 10 × 10 cm)
were cut with a band saw in direction perpendicular to the foam growth
direction. Samples were placed between two plates and the compres-
sion strength was measured as a ratio of load causing 10% deformation
of sample cross-section in the parallel and the perpendicular direction
to the square surface. The result was averaged over 5 measurements per
each sample.
Three point bending tests were carried out at room temperature,
Fig. 2. FTIR spectra of RPUFs.
137
Polymer Testing 68 (2018) 135–145
according to ASTM D7264 [31], equivalent to ISO 178 [32], using
Zwick Z100 Testing Machine (Zwick/Roell Group, Germany). Samples
were bent with a testing speed 2 mm/min. Flexural stress at break (εfB)
results for each sample were expressed as an average over 5 measure-
ments per each type of composition.
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 the tem-
perature range 20–250 °C at a heating rate of 10 °C/min, using a fre-
quency of 1 Hz and an applied deformation at 0.1%.
Water absorption of the RPUFs was measured according to ASTM
D2842 [33], equivalent to ISO 2896 [34]. 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 removed and then
blotted between dry filter paper (Fisher Scientific, USA) at 10 s and
weighed again. The average of 5 specimens was used.
Changes in linear dimensions were determined in according to
ASTM D2126 [35], equivalent to ISO 2796 [36]. Samples were condi-
tioned at 70 °C for 48 h. Length, width and thickness of the samples
were measured before and after conditioning using a vernier caliper
with an accuracy of 0.01 mm. The reported values refer to an average of
5 measurements per composition.
3. Results and discussion
3.1. Characteristics of the filler
The chemical structure of PP was determined by FTIR. The obtained
spectrum (Fig. 2) confirms the presence of reactive groups in the filler
molecule. The intense bands in the range of 1490, 1510 and 1620 cm−1
are attributed to the vibration of –COO groups, N-H bending vibration
(of secondary amines) and N–H bending vibration (of primary amines)
of protein molecules, respectively [37]. A weak broad band between
3200 and 3500 cm−1 indicates the presence of -OH groups in side
chains and terminal groups [37]. The band at 1210 cm−1 is related to
the stretching acyl groups of proteins molecules [38].
Since PP has polar groups and hydrophilic properties, strong
S. Członka et al.
Fig. 3. Particle size distribution of the filler measured after 5, 10, 15, 20 and 25 min of ultrasonic mixing.
interfacial interaction, such as hydrogen bonding, can be formed be-
tween the PP molecules and isocyanate leading to the formation of a
cross-linked structure. Amine, hydroxyl and carboxyl groups present in
PP molecules can react with isocyanates even in the absence of catalyst
[39–42]. It has been reported in previous work, that isocyanate has a
higher reactivity with amines than with hydroxyl and carboxyl groups.
The scheme of the amine reaction with isocyanate is shown in equation
(1). The reactions of hydroxyl and carboxyl groups with isocyanate
follow a similar mechanism at much slower rates forming urethane and
amide bonds as the end-products, respectively [39–42].
The results presented in Fig. 3 indicate that the filler particles ex-
hibit high tendency to agglomeration. The size of particles increases
(from 190 to 490 nm) with time, while the intensity of the peak de-
creases (from 31 to 11%), pointing to a reduced particle concentration.
After 25 min the particle size distribution shows two bands. The first
one covers diameters characteristic of primary aggregates, while the
second band evidences the presence of agglomerates. The results pre-
sented in Table 2 indicate that the average size of particles measured in
polyol is significantly higher than in water what can be connected with
swelling due to absorption of the liquid.
The result of DBPA number, expressed as the volume of dibutyl
phthalate (DBP) absorbed by specified amount of filler, is about 72.3
[ml/100 g], indicating an unbranched structure of analyzed filler. For
comparison, the DBPA value of carbon black is about 172 ml/100 g,
pointing to a large amount of free spaces between the aggregates and a
branched filler structure [43].
The viscosity of polyol premixes is a crucial parameter determining
overall quality and uniformity of foam structure [43]. The results of
viscosity of compositions modified with PP are presented in Fig. 4a. The
viscosity of the mixture rapidly increases when the concentration of PP
rises from 0.1 to 5 wt%. The viscosity increase is probably associated
with the swelling of filler particles in polyol [44]. According to the
Table 2
The average size of the filler agglomerates formed in different media (water,
polyol) and DBPA oil absorption values.
Average size of filler Average size of filler Dibutyl Phthalate
agglomerates in water agglomerates in polyol Absorption
[nm] [nm] DBPA
[ml/100 g]
1030 4280 72.3
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Polymer Testing 68 (2018) 135–145
presented results the viscosity increase from 0.1 wt% PP to 1 wt% is
large, while from 1 wt% PP to 5 wt% PP is a comparatively small
change. It can be also noticed that each of the modified system is
characterized by the same viscosity characteristics. The initial viscosity
drop is quick, whereas for the higher shear rates (about 6s−1), when the
particles of liquids reach the best possible arrangement, the viscosity
drop is significantly slower and finally becomes linear. Because the
viscosity of analyzed liquids decreases under shear strain, these fluids
can be described as shear-thinning liquids [43,45].
3.2. Foams characteristic
3.2.1. Foaming kinetics
The reaction of synthesis of PU is highly exothermic. A large amount
of heat is released in a short period of time during the gelling and
blowing reaction [46,47]. The rate of increase in temperature de-
termines the activity of reaction mixture, which in turn is associated
with the reactivity of the components of the mixture. The results pre-
sented in Table 3 indicate that the addition of small amounts of PP leads
to a significant increase of the maximum temperature (Tmax) of reac-
tion. The maximum temperature reached by the modified RPUFs in-
creases with the incorporation of PP in the formulation and is attained
at longer times (Fig. 4b). The temperature increase is likely due to the
higher concentration of reactive groups. These additional groups are
amines and hydroxyl groups introduced by PP and probably to a lesser
extent, by residual water present in the filler [48].
The foaming process was characterized by measuring the char-
acteristic processing times, cream, extension and gelation time. The
cream time was measured from the start of mixing of components to a
visible start of foam growth, the extension time until the highest vo-
lume of the foam was reached and the gelation time was the time when
the foam solidified completely and the surface was no longer tacky
[49]. The results presented in Table 3 indicate that addition of PP
changes the different characteristic times (as compared with the FR
foam) and therefore the foaming kinetics. Compared to the FR for
which cream time is about 43 s, compositions modified with PP exhibit
a slight extension of cream time, that is 49 s, 57 s and 68 s for foams
FP0.1, FP1 and FP5, respectively. According to Silva et al. [50] this
dependence is strongly connected with the fact that a well-dispersed
filler can serve as a nucleating agent in the nucleation process leading
to greater bubble formation and extend the cream time. Cream time is
also increases because the viscosity of the reaction mixture is increased
S. Członka et al. Polymer Testing 68 (2018) 135–145

Fig. 4. a) The viscosity curves of foam components and b) temperature rise during the foaming process.

Table 3
Parameters of RPUFs formation process and selected properties of RPUFs.
Foam Tmax Time [s] Apparent density [kg/m3] Thermal
[oC] conductivity [W/K∙m]
cream extension gelation upper middle bottom

FR 109 ± 2 43 ± 2 277 ± 11 341 ± 25 37.0 ± 1.1 34.2 ± 1.1 30.2 ± 0.6 0.028
FP0.1 133 ± 4 49 ± 1 339 ± 10 450 ± 22 39.8 ± 1.3 38.1 ± 0.8 36.5 ± 1.3 0.029
FP1 157 ± 4 57 ± 2 350 ± 12 442 ± 14 37.3 ± 0.9 35.4 ± 1.4 33.4 ± 1.2 0.030
FP5 160 ± 3 68 ± 2 382 ± 10 475 ± 10 36.4 ± 1.1 35.6 ± 0.7 30.2 ± 1.0 0.032

in PP-modified foams, causing more resistance to bubble expansion and
limited diffusion of gases into the bubbles. Higher viscosity can also be
the reason of longer extension time for foams modified with PP. The
higher reactivity of the system and higher temperature of reaction can
lead to a rapid increase in viscosity, decreasing the diffusion rate of
carbon dioxide and slowing the diffusion of gases into the air bubble
[51]. While, the characteristic times measured for PP-modified systems
are higher than those measured for FR foam, the obtained results are
still within the range of characteristic of RPUFs [52,53]. Similar results
of the filler's influence on the foaming process can be found in the lit-
erature. Lee et al. [54] showed that addition of carbon nanotubes
(CNTs) into water-blown PU increases the reaction time by minutes.
Prociak et al. [55] showed that modification of the reference system
with ground walnut shells increased the start and extension times by
about 60%. An increase of the total time with increasing amounts of
lignin was observed also by Arshanitsa et al. [56].
3.2.2. Cellular structure of RPUFs
One of the most important parameters of RPUFs is their cellular
structure. Morphology parameters such as cell size, wall thickness and
anisotropy, have a prominent impact on the physical and mechanical
properties of PU foams [5,57]. The structure of RPUFs, especially the
cell size and the kind of cell (open/closed) depends strongly on process
parameters like viscosity of the reaction mixture, pressure and tem-
perature gradients during the foaming process [58,59]. According to
Kang et el. [60] suitable synchronizing of the temperature of the reac-
tion with the viscosity, increases a key aspect of optimizing the blowing
process, leading to the formation of a foam with a well-developed
cellular structure. The intercellular structure of pure and PP-modified
foams is shown in Fig. 5. The structure of FR (Fig. 5a) is mostly regular
and smooth with thick struts (intercellular membrane). With increasing
content of PP in the polyol mixture (Fig. 5b–d), the foams are char-
acterized by an increasingly more inhomogeneous structure with a
higher content of open cells. Compared with FR, modified foams have a
reduced cell diameter which decreases from 316 μm to 275, 240 and
203 μm for the foams FP0.1, FP1 and FP5, respectively. This effect has
already been reported in previous works [61,62] and is attributed to the
attachment of fillers to the polymer cell wall. This attachment weakens
the cell structure, and leads to ruptures in several points [61]. Com-
pared to the FR foam, the modified foams are characterized by a wider
cell size range and higher cell distribution frequency (Fig. 6). The
widest range of cell distributions is exhibited by composition FP5.
These changes are likely due to the different temperatures which
change in viscosity, the foam kinetics and hence the structure. Foams
modified with PP are characterized by higher Tmax compared to the FR.
The temperature decrease viscosity and surface tension, leading to
thinning of the cell walls. On the other hand, the diffusion rate of CO2
gas generated from inside the foam cells outward is faster than the
diffusion rate of air into foam cells. If the expansion is too fast and cell
gas pressure becomes lower than the atmospheric pressure, the cell
walls and struts are too thin to withstand the pressure inside the cells
caused by contraction of gas (carbon dioxide) enclosed in the cells,
leading to the rupture of membrane and shrinking of the RPUFs [63].
This phenomenon is observed especially in the case of foam FP5 which
is characterized by the highest temperature of reaction. Sung and Kim
[64] explained that the alteration in the cell morphology can be also
connected with the fact that filler particles can act as a gas nucleation
sites during the foaming process and assist the formation of nucleation
centers for gaseous phase [64,65], thus affecting local rheology sur-
rounding the growing bubbles [66]. The addition of powder filler can
also change the nucleation mode from homogenous to heterogeneous
and reduce the nucleation energy, which in turn promotes the forma-
tion of large numbers of small cells [64], increasing the tendency of cell
coalescence and leading to higher inhomogeneous cell size distribution.
The same tendency noticed in this work were observed in previous
studies. The influence of soy protein on morphology of RPUFs was in-
vestigated by Zhang et al. [67]. Composite foams with 5, 10, 15 wt%
filler had a cell size of 274, 239 and 202 μm, respectively compared to
391 μm of unmodified foam. A similar trend was also observed by other
authors [68,69].

139
S. Członka et al. Polymer Testing 68 (2018) 135–145

Fig. 5. Morphology of a) FR b) FP0.1 c) FP1 d) FP5 observed parallel to the blowing direction by using an optical microscope in magnification ×250.

Fig. 6. Cell size distributions of a) FR b) FP0.1 c) FP1 d) FP5.

140
S. Członka et al.
3.2.3. Apparent density
Effects of filler addition on apparent density of RPUFs are presented
in Table 3. Results show that as the filler content increases, the ap-
parent density decreases. Changes in apparent density are closely re-
lated with the morphology changes reported in Fig. 5. Increasing PP
concentration leads to less uniform and larger cells with thinner struts,
hence to a reduced apparent density. Prociak et al. [55] explained that
the reduction of the apparent density may be due to the influence of the
filler on the reactivity of the PU system, which leads to growth of the
foam and increased volume. The authors also argued that the moisture
present in the fillers can acting as a chemical blowing agent and further
reduce density. The results presented in Table 3 also indicate that ap-
parent density is depending on the part of the sample. The density of
each foam series increases gradually from the bottom to the top part in
the PU foam rise direction. The bottom part of foam is characterized by
large holes and greater porosity due to gravity effect. Because of this the
cell growth in the bottom part of RPUFs is more than in the top part [1].
3.2.4. Thermal conductivity
One of the most important parameter of RPUFs is thermal con-
ductivity, which determines their potential use as insulating materials
[70]. Thermal conductivity of foams is governed by several factors, like
wall thickness and apparent density [47,71]. The results presented in
Table 3 indicate that introduction of PP increases the thermal con-
ductivity of foams. The thermal conductivity of the prepared RPUFs is
in the range of 0.029–0.032 W/mK which is slightly higher than idea-
lized RPUFs (0.020–0.024 W/mK) [72]. This result, however, is con-
sidered satisfactory if one takes into account that CO2 was used as
blowing agent (as opposed to the use the more thermally insulating
chlorofluorocarbon liquids, CFC, which have a harmful effect on the
environment). According to Seo et al. [73], deterioration of heat in-
sulating properties is closely related with the cellular morphology of
RPUFs. As the cell size is lower, more walls are present which inhibit
radiation. Increasing the PP content dropped the content of closed cell
content, leading to deterioration of the thermal conductivity of the
porous materials. The same tendency has already been reported by
Mosiwiecki et al. [71]. The authors showed that the thermal con-
ductivity of RPUFs modified with castor oil increases as the wood flour
concentration increases and explained that behavior considering the
increase of small and/or clustered-small cells of the reinforced foams.
3.2.5. Compressive strength
Mechanical properties of PU foams are closely dependent on the
apparent density and cellular structure. Cell morphology like cell size,
shape and anisotropy as well as the thickness of cell walls and struts
have a prominent effect on the compressive strength [74]. The influ-
ence of PP content on the mechanical properties of RPUF composites is
presented in Table 4. Compression tests were carried out in the direc-
tions perpendicular and parallel to the foam rise direction. Compression
strength in the parallel direction is significantly larger than in the
perpendicular direction, which can be ascribed to the high anisotropy
of the cells [75–77]. Compared to FR, the foams FP0.1 and FP1 exhibit
higher mechanical strength in both directions. The FR possessed the
compression strength of 187 kPa, while the sample FP0.1 exhibit the
highest compression strength of 230 kPa. When the amount of PP
Table 4
Mechanical properties of RPUFs.
Foam Compressive strength Compressive strength Flexural
(parallel) (perpendicular) strength
[kPa] [kPa] [MPa]
FR 187 ± 23 114 ± 13 0.81 ± 0.06
FP0.1 230 ± 10 120 ± 10 1.90 ± 0.06
FP1 222 ± 14 119 ± 2 0.95 ± 0.03
FP5 173 ± 15 103 ± 11 0.88 ± 0.02
141
Polymer Testing 68 (2018) 135–145
reached 1 wt%, the compressive strength slightly decreased to 222 kPa,
but still remained higher than foam FR. With higher content of filler, in
the amount of 5 wt%, the normalized compressive strength begins to
decrease and reaches 173 kPa. Compressive strength results relate to
the morphologies of Fig. 5. Foams with a large number of closed cells
with thick walls and struts can better withstand the compressive load
[74]. Besides this, even dispersion of filler in the foam rise direction
enhancing the struts and walls leads to the greater compressive
strength, especially parallel in the foam rise direction. As mentioned
previously, with increasing content of PP, the structure of modified
RPUFs becomes more inhomogeneous with a lower content of closed
cells. Furthermore, the structure is characterized by smaller cells with
thinner walls and struts. Because of this, the cell walls and struts are not
strong enough to withstand the compressive load and more stress is
generated on the cell struts, leading to deterioration of mechanical
properties of RPUFs.
The mechanical properties of modified materials are also dependent
on the interaction between the filler and the PU matrix. A high inter-
action i.e., good adhesion between the filler and the polymer matrix
makes the stress transfer between filler and the PU matrix more effi-
cient and improves the mechanical properties [78–80]. In the case of
RPUFs modified with PP, high tendency to aggregate filler particles, can
lead to a weakened interfacial adhesion between filler and effective
active surface. In consequence, RPUFs are characterized by microphase
separation of the structure, inhibiting the enhancement of mechanical
properties of obtained foams. The same tendency was observed by
Kurańska et al. [81], who investigated the impact of flax fillers on the
physico-mechanical properties of obtained composites. They noticed
that compressive strength can be decreased when a fraction of the
natural fibers is not incorporated in the struts between the cells, causing
a disordered cell structure. Madaleno et al. [82] reported an increase in
compressive strength by 20% for PU foams modified with 0.25 wt% of
montmorillonite-carbon nanotubes. With increase in filler amount, up
to 0.5 wt% and 1 wt%, the compressive strength decreases, which was
attributed to the poor dispersion of nanoparticles at higher concentra-
tions. The results obtained in the present study confirm that the addi-
tion of filler beyond a certain optimum level has a negative effect
morphology and leads to the reduction of fracture toughness and me-
chanical strength.
The compression behavior of RPUFs measured parallel to the foam
rise direction is presented in Fig. 7a. Each sample exhibits three re-
gimes: a linear elastic region, a plateau region and a densification re-
gion [61]. Compared to FR, compositions FP0.1 and FP1 exhibit more
sharp transition from the linear region (< 10% deformation) to the
plateau (around 10–25%). Composition FP5 is characterized by a more
smooth transition, which can be ascribed to a greater ductility of the
modified foam [83].
3.2.6. Flexural strength
An analysis of the results presented in Table 4 indicates that the
flexural strength of PP-modified foams slightly decreases with the in-
creased filler in mass content due to their greater elasticity, ascribed to
the cellular structure of foams. The results presented in Fig. 7b indicate
that stress-strain curves for flexural loadings are very similar, pointing
at a comparable mechanical performance of the modified foams. With
increasing content of PP, the foams exhibit an extended range of
elongation (measured as a region before fracture occurs) as a result of
greater flexibility of the PU matrix. A similar trend was observed by
Ciecierska et al. [84], who investigated the impact of carbon nanotubes
(CNTs) on the physico-mechanical properties of PU composites. They
argued that reduction of flexural strength is caused by weak adhesion
between the PU foam and filler particles as well as a nonuniform dis-
tribution of CNTs. The same tendency was also presented by other
authors [61,83].
S. Członka et al. Polymer Testing 68 (2018) 135–145

Fig. 7. a) Compression behaviors of RPUFs measured parallel to the foam rise direction b) flexural stress-strain curves of RPUFs.

Table 5 Table 6
Analysis of signal displacements in FTIR spectroscopy of characterized mate- Thermal properties of RPUFs.
rials.
Foam T10 [oC] T50 [oC] T80 [oC] Tg [oC]
N-H C=O N-H C-N
FR 266 349 522 167
Wavenumber [cm−1] FP0.1 257 365 525 147
FP1 241 359 494 137
FR 3379 1716 1506 1411 FP5 231 347 476 135
intensity 0.0022 0.018 0.023 0.010

FP0.1 3375 1709 1508 1412 with the fact, that with increasing content of filler in reaction mixture,
intensity 0.0024 0.025 0.029 0.012
the amount of water increases. Some isocyanate group react with water,
FP1 3374 1709 1509 1412 instead of hydroxyl group of polyol, and consequently, smaller number
intensity 0.0019 0.016 0.020 0.009 of urethane species is formed. A band at 1411–1412 cm−1, attributed to
C-N vibrations, indicates that composition FP1 is characterized by the
FP5 3375 1716 1507 1412
largest content of isocyanurate rings [85,90,91]. No significant shift of
intensity 0.0019 0.016 0.022 0.008
the bands attributed to the N-H stretching of the urethane group (3200-
3600 cm−1) was noticed. This suggests that PP does not interact sig-
3.2.7. FTIR analysis nificantly with PU molecules. Thus, incorporation of PP does not affect
The FTIR spectra (Fig. 2) confirm the slight difference in the che- the separation between hard and soft segments, which could lead to
mical structure of analyzed foams. The urethane moieties of PU are greater microphase separation.
confirmed by the presence of the main absorptions bands, mainly C=O
stretch (1700–1770 cm−1) [85], N-H stretch (3200–3600 cm−1) [86] 3.2.8. Thermogravimetric analysis
and N-H bend (1500-1509 cm−1) [87–89]. Signal shift and band in- Thermal stability measurements are presented in Fig. 8 and in
tensities are presented in Table 5. The FTIR spectra are extremely si- Table 6. The temperatures at 10, 50, and 80% weight losses are taken as
milar in each case, except for only differences in the intensity of some the criteria for thermal stability. Each foam presents a similar de-
bands. With increasing content of PP, the modified foams are char- gradation pattern. As the filler content in polymer matrix increases,
acterized by a lower intensity of the band at 1700-1770 cm−1 attribu- modified samples show slightly worse thermal properties, which are
table to the carbonyl group of polyurethane group. It can be connected related to the changes in cellular structure. The first step of degradation
(corresponding to the temperature at 10% of total weight losses) is
connected with dissociation of urethane bond [92,93]. With addition of
the filler, the onset of thermal degradation is lower for each series of
modified RPUFs and decreases from 257 °C down to 231 °C. It can be
ascribed to the fact that RPUFs modified with higher amount of the PP
are characterized by more ductile structure compared with FR. The
second step of degradation of RPUFs is associated with decomposition
of polyol segments [92,94]. The results indicate that decomposition
temperature is significantly affected by the amount of PP in mass
content. Foams FP0.1 and FP1 are characterized by better thermal
properties and degrade at higher temperature than unmodified foams,
while the foam FP5 exhibits slightly worse properties compared to FR.
A similar trend is observed in the third step of degradation (loss of
weight by about 80%), which is ascribed to the degradation of the
fragments generated during the second step [92,94]. Increasing the
percentage of filler reduces the thickness of walls and cell size, thereby
samples are more liable to higher temperature and exhibit worse
thermal properties. Deterioration of the thermal properties may be also
due to the degradation of PP [23]. Above 170 °C protein fragmentation
begins, leading to the damage of protein network and increasing the
Fig. 8. TGA curve of the RPURFs. thermal degradation of resulting materials [42,95]. Similar results can

142
S. Członka et al.
Fig. 9. a) Tanδ and b) storage modulus as a function of the temperature of RPUFs.
Table 7
Thermal stability of RPUFs measured by linear dimension change, weight loss during temperature exposition and water absorption.
Foam Dimensional stability [%]
length width
FR 0.90 ± 0.03 1.31 ± 0.12
FP0.1 1.39 ± 0.03 1.38 ± 0.03
FP1 1.42 ± 0.04 1.48 ± 0.07
FP5 0.76 ± 0.01 1.29 ± 0.01
be also found in literature [67,96,97].
3.2.9. Dynamic-mechanical properties
The dynamic-mechanical properties of foams are presented in Fig. 9.
Glass transition temperatures (Tg) were determined by the peak max-
imum of tanδ as a function of temperature (Fig. 9a). With increasing PP
concentration Tg decreases, from 147 °C to 135 °C (Table 6). The tanδ
peak also broadens with increasing PP concentration, which can be
attributed to the increased inhomogeneity of cellular structure with the
PP incorporation noticed in Fig. 5 [1]. With increasing filler content,
the storage modulus (E′) decreases (Fig. 9b), which can be ascribed to
the plasticizing effect of filler particles on the polymer matrix and in-
dicates weaker interactions between PU matrix and fillers. Storage
modulus is closely related to interfacial adhesion between and the
polymer matrix. Good adhesion between the filler and the polymer
matrix leads to a high cross-linked structure of resulting materials, re-
sulting in high storage modulus. Poor interfacial adhesion between
filler and PU matrix is an effect of unbranched structure of the filler and
leads to a lower storage modulus.
A different tendency as presented in this study was observed by
Formela et al. [69], who investigated the impact of spent grain and
ground tire rubber waste fillers on physico-mechanical properties of PU
composites. Addition of hybrid filler significantly increased the storage
modulus (E′) of PU and consequently the stiffness of studied composites
was also enhanced. They attributed this result to the presence of fillers
in PU foam matrix, which imposes serious limits on the mobility of
polymer chains, affecting their higher stiffness. The difference between
the results presented in previous work and the results obtained in our
research can be connected with the interactions at the PU/filler inter-
face. We attribute the difference to the fact that inorganic fillers are
characterized by smaller particles and higher specific surface area as
compared to organic fillers which facilitates better adhesion between
particles and RPUFs [96].
3.2.10. Dimensional stability and water uptake
Regarding dimensional stability, in all cases the variations in the
sample's dimensions after the thermal treatment do not follow a clearly
identifiable trend (Table 7). Overall, the changes are negligible when
143
Polymer Testing 68 (2018) 135–145
Loss in mass Water
[g] absorption [%]
Thickness
0.65 ± 0.01 0.65 ± 0.13 18.2 ± 1.2
1.12 ± 0.00 0.84 ± 0.08 14.3 ± 1.4
1.14 ± 0.05 0.82 ± 0.10 13.7 ± 2.1
1.08 ± 0.14 0.60 ± 0.09 13.6 ± 0.8
compared with the standard deviation, and thus they can be attributed
mostly to experimental errors. In each case, the dimensional stability is
still considered to be mild and within commercially acceptable limits
[98].
Water absorption of cellular materials depends mainly on cellular
morphology and on the hydrophobic nature of PU [99–101]. The open
and closed cell content as well as apparent density are the main factors
affecting foam water absorption [100]. It can be noticed that despite
the presence of higher content of open cells, the modified RPUFs absorb
less water than foam FR (Table 7). The reduced water uptake can be
attributed to the hydrophobic character of PP [14]. PP itself is water-
soluble, however after the industrial coagulation process, the protein is
damaged and aggregated, which limits its interaction with water [14].
A similar trend of fillers, preventing the penetration by water can be
also found in previous work. Kuranska et al. [44] reported that in-
corporation of microcellulose in amount to 9% into the PU system
caused a reduce of water uptake by up to 1%. In our case, water ab-
sorption in slightly higher, however, this result is still considered sa-
tisfactory for use of RPUFs as insulating materials and construction
components [102–104].
4. Conclusion
A series of RPUFs with a different content of PP were sucsessfully
synthesized. Addition of filler in the range of 0.1–5 wt% affects sig-
nificantly influence the properties of the obtained foams. The best
properties are of compositions with 0.1 wt% of PP. The modified foam
shows higher apparent density (38.1 kg/m3), greater mechanical
properties (0.23 MPa), comparable thermal conductivity (0.029 W/
m·K) and less water uptake (14.3%) as compared to the neat foam. PP
concentrations of 1 and 5 wt% result in a lower number of closed cells
and enhanced porosity. These foams, are characterized by lower ap-
parent density (35.4 and 35.6 kg/m3 respectively for FP1 and FP5),
lower compression strength (0.22 and 0.17 MPa) and higher thermal
conductivity (0.030 and 0.032 W/m∙K). The analysis of the FTIR spectra
suggests that increasing the content of the filler in polyurethane matrix
results in smaller amount of urethane moieties. Compared to the FR,
modified compositions are characterized by a lower transition glass
S. Członka et al. Polymer Testing 68 (2018) 135–145

temperature, that is, 147 °C, 137 °C and 135 °C for foams FP0.1, FP1 and C5RA00662G.
FP5, respectively. [24] ASTM D2414-Standard Test Method for Carbon Black – Oil Absorption Number
(OAN).
Incorporation of low amounts of PP appears to be a promising to [25] ASTM D2930-Standard Test Method for Low-temperature Viscosity of Automatic
improvement mechanical and physical properties of RPUFs. The de- Transmission Fluids, (Hydraulic Fluids, and Lubricants using a Rotational
velopment of PU compositions with this natural modifier could be very Viscometer).
[26] ISO 2555-Plastics - Resins in the Liquid State or as Emulsions or Dispersions -
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view, significantly increasing the range of foam applications in the in- [27] ASTM D1622-Standard Test Method for Apparent Density of Rigid Cellular
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[28] ISO 845-Cellular Plastics and Rubbers - Determination of Apparent Density.
[29] ASTM D1621-Standard Test Method for Compressive Properties of Rigid Cellular
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