applied

sciences
Article
The Effect of Accelerated Aging Conditions on the
Properties of Rigid Polyurethane-Polyisocyanurate
Foams Modified by Cinnamon Extract
Joanna Liszkowska 1, * , Krzysztof Moraczewski 2 , Marcin Borowicz 1 ,
Joanna Paciorek-Sadowska 1 , Bogusław Czupryński 1 and Marek Isbrandt 1
1 Department of Chemistry and Technology of Polyurethanes, Technical Institute, Faculty of Mathematics,
Physics and Technical Science, Kazimierz Wielki University, J. K. Chodkiewicza Street 30,
Bydgoszcz 85064, Poland
2 Department of Materials Engineering, Technical Institute, Faculty of Mathematics, Physics and Technical
Science, Kazimierz Wielki University, J. K. Chodkiewicza Street 30, Bydgoszcz 85064, Poland
* Correspondence: liszk@ukw.edu.pl; Tel.: +48-341-9382




Received: 30 May 2019; Accepted: 27 June 2019; Published: 29 June 2019


Abstract: Two series of rigid polyurethane-polyisocyanurate foams (RPU/PIR) modified by cinnamon

extract (series C_0t and CU_0t) were obtained. One RPU/PIR series contained a commercial flame
retardant (C_0t) in the formulation. The other was produced without its participation (CU_0t). The
basic properties of obtained foams, e.g., apparent density, brittleness, water absorption, compressive
strength, flammability were examined. Afterwards, both series of foams (C_0t and CU_0t) were
subjected to degradation in the climatic chamber, acting on samples of foams a defined temperature,
humidity and UV radiation for a seven days. In this way, two successive series of RPU/PIR foams
were obtained, which were designated, respectively, C_1t and CU_1t, Chosen properties of degraded
foams such as: compressive strength, cellular structure by scanning electron microscopy (SEM) and
changes of chemical structure by FTIR spectroscopy were determined. Compressive strength and
the aging resistance was also determined (against the coefficient of compressive strength variation
(CV). The possible replacement of a commercial flame retardant in polyurethane formulations by the
antioxidant raw material (cinnamon extract) was evaluated.

Keywords: rigid PU/PIR foam; DSC; FTIR; degradation; climatic chamber; flame retardant;
cinnamon extract

1. Introduction
The field of polyurethanes (PU) is one of the fastest growing fields of polymer technology. Intensive
research is conducted to modify their properties for meeting the requirements of customers [1]. Foams
used in civil engineering as construction or insulation materials require adequate strength, resistance to
aging and weather conditions, dimensional and thermal stability, and fire resistance [2,3]. The literature
presents issues related to the possibility of delaying the burning of foams, improving dimensional
stability, insulating and mechanical properties [4–6]. Possibility of modifying of polyol premixes by
biopolyols, improves some properties of PU foams [7–9]. Many renewable sources are used for the
development of polyurethane foams (PUF) and other PU products. Polyols, a raw material of PU
foam, have been also derived from different renewable sources, e.g., from vegetable oils, sugarcane
bagasse, and pine wood. These bioproducts are used to produce environmentally friendly PU products.
Additionally, ground coffee waste could be used in acid liquefaction polyhydric solvents (e.g., PEG
400/glycerol, 90/10 wt/wt) in the presence of sulfuric acid [10,11]. Thermogravimetric analysis (TGA)
confirmed that these bio-based PUFs were thermally stable up to 190 ◦ C. Foams regained their original

Appl. Sci. 2019, 9, 2663; doi:10.3390/app9132663 www.mdpi.com/journal/applsci

Appl. Sci. 2019, 9, 2663 2 of 23

shape even after 70% of creep compression, which showed their good elastic behavior. They can be
used as thermal and acoustic insulation, even in aeronautics.
Antioxidants (e.g., lactone-based, phenols in combination with phosphites or tioesters) could
decrease the scorch. A large number of factors may promote scorch in flexible foams: high water
content in the formulation, a high isocyanate index, FR additives, pigments, methylene chloride-based
blowing agent, high ambient humidity, collapsed foam layers, air flow, smaller size of cells, foam block
size, metal traces, hydroperoxides, or free ethylene oxide content of polyol. Pentabromodiphenyl oxide
blended with aromatic phosphates showed higher thermal and hydrolytic stability did not promote a
scorch of flexible PUFs [12].
Factors such as thermal, electrical, electrochemical aging, mechanical, environmental exposure,
and others have a significant influence on the decrease of the properties of insulating materials during
their handling. The phenomenon of decreasing properties with time lapse is called aging or lack of
resistance (durability) to climate change. In order to prevent it, additive agents (so-called antioxidants)
are added.
Aging of materials is structural changes occurring in the whole mass of the material, in the long
time. It usually leads to the decrease of their functional properties. The basic factors causing aging
are: temperature, sunlight, humidity, chemical agents, and microorganisms. The behavior of the
material under the influence of these factors during it using is difficult to predict [13,14]. It is difficult
to distinguish a dominant degradation factor during aging under natural climatic conditions, because
all of its affect simultaneously [15]. The most common changes occurring in the polymer during the
aging process are: crosslinking, oxidation (thermooxidation), degradation, and destruction.
The concepts of resistance and durability are very often used in the description of aging
materials. Hardiness is a material resistance that it puts into action by specific destructive chemical,
physico-chemical, physical, or biological factors. Durability is the average time after which the selected
material property becomes extremely permissive as a result of aging processes, i.e., it reaches a critical
level. The critical level is defined as the determined absolute value of the measured quantity or
the percentage change of this value in relation to its initial value. The aging time is also taken into
account [16].
Accelerated aging is the process that is most often carried out to estimate the resistance to a
decrease of the parameters of the tested material over time. This is a simulation of natural aging in a
shortened time. Subjecting plastics to accelerated aging causes a decrease in mechanical properties,
e.g., strength [3,17]. Aging of polyurethane foams is tested mainly by measuring changes of linear
dimension, geometric volume, and mass after 48 hours of thermostating in a dryer with forced
circulation [1,18]. The smallest change in dimensions or the volume of foam is extremely important in
using it as thermal insulation. Properly selected industrial insulation affects not only the saving of
energy costs, but also the correct operation of the technological installation [19].
PUFs’ aging can also take place under conditions of simulated solar radiation, so-called
photodegradation [9], and in a climatic chamber [20]. Polyphenols contained in cinnamon extract are
used also in cosmetics, coffee, tea or cocoa, and as anti-oxidants to prevent the aging process [21,22].
Phenolic antioxidants are used for polyolefins [23].
The aim of the study was to determine the effect of cinnamon extract in synergy with a flame
retardant (Antiblaze TCMP) on the structure, aging, and mechanical and functional properties of
RPU/PIR foams. The influence of this biofiller on the properties of foams without flame retardant was
also examined. Antiblaze TCMP contains in its composition chlorine and phosphorus [24], compounds
of this type are currently limited due to the negative impact on the natural environment [25].
In relation with the above, the possibility of replacing a commercial flame retardant with a
cinnamon extract (used until now in the cosmetics industry) has also been checked. The obtaining
polyurethane-polyiscoyanurate (RPU/PIR) foams were also subjected to an accelerated aging tests two
ways (air dryer and air conditioner) [26,27]. Among others, the analysis of foams before and after aging
Appl. Sci. 2019, 9, 2663 3 of 23

in infrared spectroscopy (FTIR) and the analysis of their structure by scanning electron microscopy
(SEM) was also performed.

2. Materials and Methods

2.1. Materials
Rokopol RF-551, a sorbitol oxyalkylation product (PCC Rokita S.A., Brzeg Dolny, Poland),
was used as a reference polyol (hydroxyl number 420 mg KOH/g, molecular weight = 650 g/mol,
functionality 4,5), to prepare RPU/PIR foams. Catalytic system in the RPU/PIR formulation were
33% solution of anhydrous potassium acetate (Chempur, Piekary Ślaskie, ˛ Poland) in diethylene
glycol (Chempur, Piekary Ślaskie,˛ Poland), as a trimerization catalyst and 33% solution of
DABCO—1,4-diazabicyclo[2.2.2]octane (Alfa Aesar, Haverhill, MA, USA) in diethylene glycol—as a
polyurethane bond catalyst. The stabilizer of the foam structure was poly (oxyalkilene siloxane)
surfactant Tegostab 8460 (Evonik, Essen, Germany). Carbon dioxide produced in situ in the
reaction between water and isocyanate groups was a blowing agent. Furthermore, a commercial
flame retardant, Antiblaze TCMP—tris-(2-chloropropyl) phosphate (Albemarle, Charlotte, NC,
USA)—was added into some of the foams. The isocyanate raw material was a technical polymeric
diisocyanate Purocyn B (supplied by Purinova, Bydgoszcz, Poland), whose main component was
4,4’-diphenyl-methane-diisocyanate (MDI). The density of Purocyn B at a temperature of 25 ◦ C was
1.23 g/cm3 , viscosity was 200 mPas, and content of –NCO groups was 31.0%. Polyether and diisocyanate
were characterized in accordance with appropriate standards like ASTM D 2849-69 and ASTM D
1638-70. Cinnamon extract—CE (Agrema Sp. z o.o., Wroclaw, Poland)—was used as a physical
filler. According to the manufacturer information, this extract contains 5% of polyphenols. The main
polyphenols in the cinnamon extract were, respectively, chlorogenic acid, flavonoids, and phenolic
acids. In this biofiller are also metals in trace amounts (Table 1). The rest of the extract was an
inert carrier of the active substances (polyphenols) [28]. Cinnamon was analyzed by FTIR technique
(Figure 1). Cellulose in cinnamon comes from the bark of a cinnamon tree.

Table 1. Cinnamon extract composition.

Compound Content
(a) polyphenols
Chlorogenic acid together
5%
Flavonoids
Phenol acids
heavy metals
lead 0.49 ppm
(b) cadmium 0.15 ppm
arsenic 0.81 ppm
mercury 0.09 ppm
chromium 1.06 ppm
chloride 0.51 ppm
sulphate 3.00 ppm
(c) carrier of the active substance (cellulose) about 94.9%

FTIR analysis of cinnamon (Figure 1) showed the presence of groups –OH (3346.25 cm−1 ) and
–C-H (2928.26 cm−1 , 1416.64 cm−1 , 1367.87 cm−1 , 848.63 cm−1 ) derived from –CH2 OH or from the ring
in cellulose; the aromatic ring (1631.68 cm−1 , 763.47 cm−1 , and 707.31 cm−1 ) derived from cellulose,
flavonoids, and phenol acids; and 1152.23 cm−1 represents the aromatic ether from flavonoids. –OH
groups can be largely derived from cellulose.
 Appl. Sci. 2019, 9, 2663 4 of 23
Appl. Sci. 2019, 9, x 4 of 23

127
128 Figure1.1.FTIR
Figure FTIRanalysis
analysisofofcinnamon
cinnamonextract.
extract.

2.2. Synthesis of the Rigid PUR-PIR Foams

129 2.2. Synthesis of the Rigid PUR-PIR Foams
Foam formulations (Table 1) were calculated based on the reference sources [1,29]. Detailed
130 Foam formulations (Table 1) were calculated based on the reference sources [1,29]. Detailed
calculations are provided in cited articles [30,31]. The basic components of the foams are: polyol and
131 calculations are provided in cited articles [30,31]. The basic components of the foams are: polyol and
polyisocyanate. Two types of catalysts are used: amine (Dabco) and organometallic (Catalyst 12).
132 polyisocyanate. Two types of catalysts are used: amine (Dabco) and organometallic (Catalyst 12). The
The first one catalyzes crosslinking reactions, the second accelerates the reaction of isocyanate groups
133 first one catalyzes crosslinking reactions, the second accelerates the reaction of isocyanate groups
with hudroxyl groups. Tegostab surfactant is necessary to stabilize the structure of foams, facilitating
134 with hudroxyl groups. Tegostab surfactant is necessary to stabilize the structure of foams, facilitating
the mixing of ingredients. Water was used as the foaming agent, which forms CO2 in reaction with
135 the mixing of ingredients. Water was used as the foaming agent, which forms CO2 in reaction with
the –NCO groups [29]. PUFs were prepared at a laboratory scale by a one-step method from the
136 the –NCO groups [29]. PUFs were prepared at a laboratory scale by a one-step method from the two-
two-component system (A and B) in the mass equivalent (R) ratio of NCO groups to OH groups equal
137 component system (A and B) in the mass equivalent (R) ratio of NCO groups to OH groups equal
3,7:1 [29]. An increased amount of polyisocyanate (3.7 R instead of 3.0 R) was used for the reaction
138 3,7:1 [29]. An increased amount of polyisocyanate (3.7 R instead of 3.0 R) was used for the reaction of
of polyisocyanate with water. The NCO group chemical equivalent (R) was calculated according to
139 polyisocyanate with water. The NCO group chemical equivalent (R) was calculated according to
Equation (1):
140 Equation (1):
4200
RNCO = (1)
4200
31%NCO
𝑅 = (1)
where %NCO is the content of the NCO group in the 31%NCO
polyisocyanate raw material (%).
141 The%NCO
where hydroxyl group
is the chemical
content of theequivalent
NCO group (R)inwas
thecalculated according
polyisocyanate to the following
raw material (%). equation:
142 The hydroxyl group chemical equivalent (R) was calculated according to the following equation:
56100
ROH = 56100 (2)
𝑅 = HN (2)
HN
where HN is the hydroxyl number of Rokopol RF-551 (mg KOH/g).
143 where HN is the hydroxyl number of Rokopol RF-551 (mg KOH/g).
The component A (polyol premix) was obtained by the precise mixing of the suitable amounts of
144 The component A (polyol premix) was obtained by the precise mixing of the suitable amounts
Rokopol RF-551 (66.80 g) trimerization catalyst (8.00 g), polyurethane bond catalyst (3.20 g), flame
145 of Rokopol RF-551 (66.80 g) trimerization catalyst (8.00 g), polyurethane bond catalyst (3.20 g), flame
retardant (47.60 g), surfactant (5.40 g), chemical blowing agent (CO2 (distilled water was used in an
146 retardant (47.60 g), surfactant (5.40 g), chemical blowing agent (CO2 (distilled water was used in an
amount of 3.15 g)), and biofiller. Ground cinnamon extract was added in amounts of 5 wt%, 10 wt%,
147 amount of 3.15 g)), and biofiller. Ground cinnamon extract was added in amounts of 5 wt%, 10 wt%,
and 15 wt% (Table 2). The selection of fillers and flame retardants was made on the basis of the symplex
148 and 15 wt% (Table 2). The selection of fillers and flame retardants was made on the basis of the
planning triangle [32]. The considered premixes contained a variable amount of cinnamon extract and
149 symplex planning triangle [32]. The considered premixes contained a variable amount of cinnamon
a constant amount of flame retardant (C_0t series) or a variable amount of cinnamon extract without
150 extract and a constant amount of flame retardant (C_0t series) or a variable amount of cinnamon
flame retardant (series CU_0t). Two reference premixes without fillers were also obtained: W_0t (with
151 extract without flame retardant (series CU_0t). Two reference premixes without fillers were also
flame retardant) and WU_0t (without flame retardant). Component B was polyisocyanate Purocyn B
152 obtained: W_0t (with flame retardant) and WU_0t (without flame retardant). Component B was
in the amount of 250.60 g. Both components A and B were mixed (1800 rpm, 10 s) at their respective
153 polyisocyanate Purocyn B in the amount of 250.60 g. Both components A and B were mixed (1800
154 rpm, 10 s) at their respective mass ratios and poured into an open cuboidal mold with internal
Appl. Sci. 2019, 9, 2663 5 of 23

mass ratios and poured into an open cuboidal mold with internal dimensions of 190 × 190 × 230 mm.
Two series of modified foams (C and CU) and two reference foams (W and WU) were obtained.

Table 2. Formulation of RPU/PIR foams.

Foam Ground Cinnamon Extract (g) Antiblaze TCMP (g)

W_0t 0.0 54.0
WU_0t 0.0 0.0
C5_0t 15.9 54.0
C10_0t 31.8 54.0
C15_0t 47.6 54.0
CU5_0t 15.9 0.0
CU10_0t 31.8 0.0
CU15_0t 47.6 0.0

2.3. Methods

2.3.1. Foaming Process

The foaming process was analyzed in accordance with ASTM D7487 13e—Standard Practice for
Polyurethane Raw Materials: Polyurethane Foam Cup Test [33]. Measured by electronic stopwatch
to determine the characteristic foaming times in accordance: cream time: from the start of mixing
components A and B until fine bubbles appeared; free rise time: from the start of mixing components
A and B until the foam stops expanding; string gel time: from the start of mixing components A and B
until long strings of tacky material can be pulled away from foam surface when the surface is touched
by a tongue depressor; and the tack-free time: from the start of mixing components A and B until
the foam surface can be touched by a tongue depressor without sticking. The maximum reaction
temperature (Tmax ) in the foams was measured during its synthesis by using a thermometer placed in
the center of the obtained RPU/PIR foams.

2.3.2. Foam Aging was Carried Out Using Two Methods

Accelerated Aging Tests

Accelerated aging tests of the RPU/PIR foams was carried out by the thermostating process of
a cubic specimen with a side length of 50 mm in 48 h at temperature of 120 ◦ C. The samples were
thermostated in a dryer with forced air circulation. The result of this test were change of linear
dimensions (∆l), change of geometrical volume (∆V), and mass loss (∆m). Values of these parameters
were calculated in accordance with ISO 1923: 1981 and PN–EN ISO 4590: 2016-11. The formulas for
calculations ∆l, ∆V, ∆m are shown in Equations (3)–(5):

l − l0
∆l = ·100% (3)
l0

where l0 is the length of the sample before thermostating, according to the direction of foam rise (mm),
and l is the length of the sample after thermostating, according to the direction of foam rise (mm).

V − V0
∆V = ·100% (4)
V0

where V0 is the geometrical volume of the sample before thermostating (mm3 ), and V is the geometrical
volume of the sample after thermostating (mm3 ).

m0 − m
∆m = ·100% (5)
m0
Appl. Sci. 2019, 9, 2663 6 of 23

where m0 is the mass of the sample before thermostating (g), and m is the mass of the sample after
thermostating (g).

Aging in a Climate Chamber

Aging in a climate chamber consisted of the controlled submission of samples to treatment
destructive factors, i.e., increased temperature, humidity, and UV radiation, at the same time. This
mechanical property plays a significant role during the using of foams in civil engineering, especially
in structural applications [15]. Aging due to the action on samples of heat foams, UV radiation, and
moisture was marked in a set time interval of seven days (the series was marked C_1t and CU_1t).
The cubic specimens with a side length of 50 mm were also separately aged during the seven days
(for compressive strength tests). It consisted in placing samples in a heated heating chamber up to
50 ◦ C, 70% relative humidity, and irradiance of 320.86 W/m2 . For aging tests, the climate chamber
(DYCOMETAL CCK, model CCK-40/300 NG, Es-tor L.T.D., Poznań, Poland) was used for tests with
artificial light with UV lighting. The chamber has 8 fluorescent lamps (PHILIPS SUPER ACTINICA TL
60 W / 10-R ISL). The fluorescence wavelength range was between 350–400 nm) [34]. The dimensions
of the chamber were 0.572 m × 0.654 m. Heating was set at 4 ◦ C/min for the first hour according to
IEC 60068-3-5 (for an empty chamber). Then, the temperature was kept constant for a certain time
(seven days). Samples were placed directly under the lamps, so that the sample distance the lamp
was as small as possible. The radiation from the lamps fell at an angle of 90◦ to the surface of the
samples. The heating was carried out in a continuous mode, without opening the chamber. This
action was aimed at deteriorating the physico-mechanical properties of the samples tested [18]. This
does not fully reflect the changes that occur during the natural aging process, but it is sufficient to
quantify decrease of samples strength coefficient of compressive strength variation (CV) and to assess
the effect of given degradation conditions on DSC and strength. The samples were removed from the
chamber after ending of the heating and one week degradation). The degraded area was evaluated
for selected properties of ambient conditions. The obtained results of selected tests of one-week-aged
foams (series 1 t) and results of pre-aging tests in a climatic chamber (series 0 t) were compared. In this
way, the combined effect of temperature, UV radiation, and moisture on selected foam properties
(compressive strength, DSC, FTIR, change of linear dimensions, change of geometrical volume and
mass loss) was determined.

2.3.3. Apparent Density

The apparent density of the obtained foams was determined as the ratio of foam weight to its
geometrical volume, using cubic samples with side length of 50 mm in accordance with the ISO
845:2006 standard.

2.3.4. Flammability Tests

A simplified flammability chimney test (called also Bütler’s combustion test or vertical test) was
carried out in accordance with ASTM D3014-04. The apparatus used for this flammability test consists
of a vertical column with dimensions 300 × 57 × 54 mm where three walls are made of sheet metal,
and the fourth is a movable window. The test was performed on six specimens with dimensions of
150 × 19 × 19 mm. Before combustion the sample was weighed to an accuracy of 0.0001 g, then it
was placed inside the chimney. The samples were burned by the flame from the burner fueled by
propane-butane gas mixture at a time of 10 s. Then the burner was moved away. Combustion residue
was calculated according to Equation (6):
mb
CR = ·100% (6)
ma

where ma is the mass of the sample before burning test (g), and mb is the mass of the sample after
burning test (g).
Appl. Sci. 2019, 9, 2663 7 of 23

Flammability was tested based on a marker method in accordance with the PN–EN ISO 4589-2:2006
standard by a Limited Oxygen Index Module apparatus (Concept Equipment, Phoenix Court,
Rustington, Great Britain). This test determined the boundary percentile volume of oxygen in a
mixture of oxygen and nitrogen needed for sustaining the burning of the sample 150 × 13 × 13 mm in
dimension. The limited oxygen index in percentage by volume of oxygen in the mixture is determined
from Equation (7):
[ O2 ]
LOI = ·100% (7)
[ O2 ] + [ N2 ]
where O2 is the volumetric flow rate of oxygen (m3 /h), and N2 is the volumetric flow rate of
nitrogen (m3 /h).
Another burning test was conducted by using the horizontal method according to the PN-78
C-05012 standard. This method marked the speed of surface flame spreading on a sample
150 × 50 × 13 mm dimensions, which was placed horizontally and exposed to a flame at one of
end. The flame was also from the burner fueled by the propane-butane gas mixture. The speed
of surface flame spreading is a speed at which the head of the flame moved on the surface of the
flammable sample. During the test the sample foam was placed on a net in a horizontal position and a
burner was placed at one side of the foam’s end for 60 s. A line was drawn across the 125 mm mark
from the side where the burner was placed. The distance of the flame and the time to reach the marked
line need to be noted. If the foam extinguishes before the flame reaches the marker, then the foam is
categorized as self-extinguishing. If the foam keeps burning, an average burning time of the marked
distance can be determined or the speed of flame spreading (in mm/s) based on the distance the head
of the flame covers in a specific time. Flammability of foams was classified according to PN–EN ISO
3582:2002.

2.3.5. Differential Scanning Calorimetry (DSC)

Changes occurring in foams under heat was checked by differential scanning calorimeter DSC
Q200 (TA Instruments, New Castle, DE, USA) with built-in Advanced Tzero technology. The apparatus
working range was from –90 to +725 ◦ C (foam tests were conducted in the range from 0◦ C to 400 ◦ C)
in one-step heating, under nitrogen flow. The mass of a sample was 2.9–3.1 mg.

2.3.6. Softening Point

Thermal properties of the foams are determined by measuring of their softening point. The Vicat
apparatus was used for this temperature measurement. The softening point, as the thermal resistance
to compression, was marked by using cubic samples with 20 mm edge (according to the foam rising
direction) in accordance with DIN 53424 standard. Foam samples were subjected to compressive load
of 24.52 kPa at 50 ◦ C temperature for an hour. The softening point is the temperature at which the
sample was compressed by 1 mm.

2.3.7. Compressive Strength and Compressive Strength Ratio

Compressive strength was measured using an Instron universal strength machine 5544 according
to PN-93/C-89071 (ISO 844). The compressive strength of foams before degradation (0t series) and after
seven days of degradation (1t series) was tested. The aging resistance in relation to the coefficient of
variation of compressive strength (CV) was calculated from Equation (8) [15,35] in accordance with
ISO 844:2014:
W
CV = ·100% (8)
W0
where W0 is the compressive strength measured before foam degradation (kPa), and W and compressive
strength measured after foam degradation (kPa).
Appl. Sci. 2019, 9, 2663 8 of 23

2.3.8. Foam Structure

The foam structure was determined by Hitachi TM 3000 SEM with EDS attachment (Hitachi
High-Technologies Co., Tokyo, Japan). The samples were dusted with a gold layer that was about 6
nm thick. The studies were performed at the accelerating voltage of 10 kV, with the working distance
10 mm and magnification at 50×. The statistical analysis of cell sizes was carried out on the basis of
obtained micrographs by using ImageJ software (LOCI, Madison, WI, USA).

2.3.9. Absorbability and Water Absorption

Absorbability (A) and water absorption (WA) were determined in accordance with ISO 2896:2001,
measured after immersion in distilled water for 24 h. Values of these parameters were calculated from
Equations (9) and (10):
m − mD
A= A ·100% (9)
mD
where mA is the mass of the sample after immersion in distilled water (g), and mD is the mass of the
dry sample (g).
m − mD
WA = WA ·100% (10)
mD
where mWA is the mass of the sample after surface drying (g).

2.3.10. Brittleness
Brittleness was measured according to ASTM C-421-61. Based on the quoted norm, brittleness
was calculated as a percentage weight loss of 12 foam cubes (shape of cubes with a side of 25 mm). The
brittleness test was carried out in a normalized device, which was a cubic chest made from oak wood
with dimensions 190 × 197 × 197 mm. This device was rotated around the axis at 60 rpm. The filling
of the chest consisted of 24 oak cubes with side length of 20 mm. The loss of foam weight in percent
reflected the value of its brittleness. This parameter was calculated on the basis of Equation (11):

m1 − m2
K= ·100% (11)
m1

where m1 is the mass of the sample before test (g), and m2 is the mass of the sample after test (g).

2.3.11. Chemical Structure

The chemical structure of the obtained foams was evaluated on the basis of infrared spectra
obtained by using the Nicolet spectrometer iS10 FTIR spectrophotometer (Thermo Fisher Scientific,
Waltham, MA, USA). It has a spectrospcopic range from 7800 to 350 cm−1 and a maximum resolution
capability of < 0.4 cm−1 with a DTGS detector.

2.3.12. Content of Closed Cells

The samples before testing the contents of closed cells were seasoned by 24 h. The test of this
parameter was carried out in accordance with the PN–EN ISO 4590:2016-11 by using the helium
pycnometer AccuPyc 1340 with the FoamPyc software from Micrometrics Instrument Corporation,
Norcross, USA. This software calculated the content of closed cells based on the measurement of
pressure changes in the test chamber.

2.3.13. Measurement of Foam Color

A standard colorimetric observer (2◦ ), Konica Minolta CR-410, with D65 light source and calibration
according to white pattern, produced by Konica Minolta Sensing Americas, Inc, 101 Williams Drive
Appl. Sci. 2019, 9, 2663 9 of 23

Ramsey, NJ 07446 USA. The device gives the average of three measurements L, a, and b. The difference
between the two colors in the space (∆E) was calculated according to Equation (12):
q
∆E = (∆L)2 + (∆a)2 + (∆b)2 (12)

where L is the vertical axis of the coordinate system defining the brightness; a is the axis of the
coordinate the amount of red (positive “a” values), the amount of green (negative “a” values); and b is
the axis expressing the amount of yellow color (positive values) or blue (negative values) in color.

3. Results and Discussion

3.1. Foaming Process

The course of the foaming process depends on the raw materials used [36]. Development of
the correct composition of the polyol mixture of RPU/PIR foam allows obtaining a product with the
desired properties [37]. The foaming agent used in the foaming process has a great influence on the
thermal insulation properties of the foams. A suitable catalytic system and surfactant give a cellular
structure that ensures the stability of the performance-usable parameters. Two different series of
foams were synthesized according to the formulations presented in Table 1. The basic technological
parameters of the foaming process of modified PU premixes are characteristic times. Synthesis of
RPU/PIR foams was monitored by measuring the appropriate processing times by using an electronic
stopwatch. Result of this measurement were shown in Table 3. Addition of a modifier in the form of
cinnamon extract contributed to the prolongation of the processing parameters of RPU / PIR foams.
Cream times for both of foams series were elongated from 8 s for foam W_0t and WU_0t to 10 s for
foams with content of cinnamon extract (foams C series and CU15_0t). Free rise times were also
increased from 34 s (for reference foams) to 54 s (C15_0t, foam with 15 wt% of cinnamon extract) and
to 44 s (CU15_0t, foam with 15 wt% of cinnamon extract without flame retardant). String gel times
were extended about 7 s (for C foams) and about 10 s (for CU foams) in compared with W 0t and
WU_0t foam. Modifier cinnamon extract (CE: 5% wt., 10% wt., 15% wt.) influenced the viscosity of
the initial mixture. The foaming process was partially disrupted, because the processing parameters
slightly increased. There were probably additional reactions between –OH and –COOH groups (from
CE) with the isocyanate, thus creating an imbalance in the NCO/OH ratio. This also manifested in the
increase in Tmax -modified foams according to the reference foams (Table 3) [38]. Maximum reaction
temperatures were increased by about 17–25 ◦ C for modified foams. The process of free growth of
the foam and its gelation was disturbed by the addition of cinnamon extract. The free rise time and
string gel time increased (respectively, from 34 s to 54 s and from 23 s to 33 s). Elongation of these
times is advantageous when obtaining foams in complicated shapes, in which the polyol mixture must
thoroughly fill the entire mold.

Table 3. Processing times of RPU/PIR foams (0t series).

Free Rise Time String Gel Tack Free Time

Foam Cream Time (s) Tmax (◦ C)
(s) Time (s) (s)
W_0t 8 34 23 21 126
WU_0t 8 34 23 21 125
C5_0t 10 46 28 24 151
C10_0t 10 48 30 25 146
C15_0t 10 54 30 26 148
CU5_0t 9 36 25 24 144
CU10_0t 9 40 26 25 144
CU15_0t 10 44 33 27 142
 Appl. Sci. 2019, 9, 2663 10 of 23

3.2. Organoleptic Assessment of RPU/PIR Foams

An oraganoleptic analysis was performed comparing the appearance of non-degraded foams
(series 0t on photographs in Figure 2a) with foams aged in a dryer at 120 ◦ C for 48 h (C and CU, WU
and WU series 48h on photographs in Figure 2b) and with foams degraded in the climatic chamber (1t
series in Figure 3). The external appearance of the foams and the possible color change were compared.
It was determined whether the surface of the foams are crumble or not. Foams after thermostating in
the dryer had a slight change in their color (foams in Figure 2b) in relation to the non-thermostated
foams (Figure 2a). Aging at temperature (120 ◦ C) caused a light yellow foams color (Figure 2b). Their
Appl. Sci. 2019, also
roughness 9, x increased. 10 of 23

347
348 (a)

349
350 (b)
351 Figure
Figure2.2.Photography
Photographyofoffoam
foamseries:
series:(a)
(a)C_0t
C_0tand
andCU_0t
CU_0tnot
notdegraded;
degraded;and
and(b)
(b)C_48h
C_48hand
andCU_48h
CU_48h
352 aged in a hot air dryer (48 h, 120 °C).
◦
aged in a hot air dryer (48 h, 120 C).

353 The surface color of foams, which were irradiated by UV rays in the climate chamber, was
354 changed from light yellow to orange (series C_1t on Figure 2). After that, the surface was exposed to
355 UV radiation, humidity, and temperature. The surface of C_1t and W_1t foams became brittle after
356 degradation than the surface of CU_1t and WU_1t foams. The following dependence was observed:
357 CU_0t foams not contained the flame retardant (FR) were more brittle than the C_0t foams that
 Appl. Sci. 2019, 9, 2663 11 of 23
Appl. Sci. 2019, 9, x 13 of 23

420
421 Figure 3. Foams of series 1t, degraded in the climatic chamber (one week).
Figure 3. Foams of series 1t, degraded in the climatic chamber (one week).
422
The surface color of foams, which were irradiated by UV rays in the climate chamber, was changed
423 Table 6. Compressive strength (CS) and compressive strength ratio (CV): CS_0t—measured before
from lightcondition;
424 yellow toCS_1t—measured
orange (series after
C_1tone-week
on Figure 3. After that, the surface was exposed to UV radiation,
condition.
humidity, and temperature. The surface of C_1t and W_1t foams became brittle after degradation
than the surface of CU_1t andFoam WU_1t foams. CS_0tThe followingCS_1t dependence CV was observed: CU_0t foams
(kPa) (kPa) (%)
not contained the flame retardant (FR) were more brittle than the C_0t foams that contained FR.
W 251.6 ± 6 140.5 ± 4 74.7 ± 2
Degradation caused the opposite effect. Crumbling of the surface of a series of foams (CU_1t, without
WU 361.4 ± 9 256.2 ± 6 70.9 ± 2
flame retardant after one weekC5 of degradation)
212.7 ± 6
slightly increased. 94.1
200.1 ± 5
Surface
±2
of C_1t foams subjected to
one week of degradation was much C10 more destroyed
160.4 ± 4 than the
143.9 ± 4surface of foams
89.7 ± 2 from before degradation
(C_0t). Based on the organoleptic C15assessment,
147.3 ±it 3could126.6be assumed
±4 that ±the
86.0 2 removal of flame retardant
from cinnamon-based foams should CU5 improve
121.4 ±the 3 strength
151.1 ±of4 the bonds
124.4 ± 3responsible for reducing the
crumbling of CU_1t foams in relation CU10 to the109.4 ± 2 series132.8
C_1t ±4
subjected to121.4
aging± 3in the climatic chamber. The
CU15 91.9 ± 2 109.6
color change can be caused by thermal-oxidation degradation of the foams ± 3 119.2 ± 3 surface, hence, the color
change in the case of thermostating (foams on Figure 3).
425 3.6. FTIR Analysis
Wirpsza [29] reports that PU obtained from aromatic MDI turn yellow under the influence of
426 Susceptibility
light. Colorful to degradation
quinonoimide depends
groups are formed onon theitspresence
surface. of specific chemical
Yellowing does not groups in strength
affect the the
427 molecule.
properties, Thedecreases
it only easily hydrolysable
the propertiesester, amide, and urea groups accelerate the polymer
of coatings.
428 A decomposition
different color [39,40]. Sinceorange)
(yellow, photodegradation
was observed of polymeric materialsoftakes
on the surface place most
conditioned intensively
foams (Figure 3)
429 in the surface layer, up to approx. 10 μm [41], the surface of degraded foams was scraped (1t series)
depending on whether the foam contained a flame retardant (yellow) or not (orange). This dependence
430 and FTIR spectra of 1t foams were compared with the 0t series spectra (not subjected to degradation).
was already observed in reference foams (W_1t and WU_1t) even before the addition of cinnamon
431 On the basis of the FTIR analysis (Figure 3a,b), the following groups (Table 7) can be distinguished
extract.
432 Softconstruction
in the segments of of the foams,N–H,
all foams: which
CH,are aliphatic
–N=C=O, polyethers
–N=C=N, C=O in and aliphatic
urethane, polyesters,–C=N
isocyanurate, are more
susceptible
433 to oxidation and affect discoloration (change of color) [12]. Aromatic
in the trimer, and C–O. The polyurethane-polyisocyanurate structure of the obtained foams has been amines are produced
434
in theconfirmed
reaction of the isocyanate with water. They are easily oxidized to chromophores could make
[1,5,8].
to contribution towards change of color of foams. The changed color on the surface of C_0t series
435
can be caused by presence of phosphate Table 7.flame
Resultsretardant.
of the FTIR These
analysis.compounds can decompose giving

hydrogen halide. Band, cm–1 Bond

3325 N–H
3.3. Color of Foam 2930 C-H
2276 –N=C=O
Foam color test results are included in Table 4. The test results showed a practically small increase
2137 –N=C=N–
in the brightness of the foams at once with increasing cinnamon extract content in unheated and
non-conditioned foams (brightness L was from 82.825, in foam W_0t to 66.735, in C15_0t foam). At the
same time, these foams contained more red (a) and yellow (b). The L range was from 71.400 (W_48h)
to 62.625 (CU5_48h) for foams aged in the dryer within 48 hours. At the same time, the content of
Appl. Sci. 2019, 9, 2663 12 of 23

red and blue color increased in them. Foams conditioned in the air conditioner (series 1t) resulted in
the reduction of the L factor (50.78–57.285) and in the increase in parameter a in the range from 13.68
to 21.635 in relation to a parameter of the 0t series (from −3.625 to 3.420). The ∆E parameter of 48 h
thermostated foams was from 68.138 to 77.132 and conditioned foams (1t series) was from 59.998 to
62.444 in relation to the value of ∆E of 0t series (from 72.772 to 87.461).

Table 4. Foam color measurement results.

Foam L a b ∆E
W_0t 82.8 −2.6 28.0 87.5
C5_0t 85.1 0.5 14.9 86.4
C15_0t 76.6 3.4 15.8 78.3
WU_0t 81.8 −3.6 27.0 86.2
CU10_0t 71.0 2.7 15.9 72.8
W_48h 71.4 8.4 27.9 77.1
C5_48h 70.7 6.8 27.3 76.1
WU_48h 58.7 15.8 35.1 70.2
CU5_48h 62.6 5.9 23.1 67.0
CU15_48h 65.2 5.6 19.1 68.1
W_1t 56.4 18.2 17.3 61.8
C5_1t 57.3 17.4 16.1 60.1
C15_1t 50.8 21.6 29.2 62.4
WU1_t 56.3 16.0 21.3 62.3
CU5_1t 53.4 16.7 21.7 60.0
CU15_1t 57.1 13.7 18.1 61.4

3.4. Accelerated Aging Tests

The literature [14] states that aging of elastic porous materials does not lead to dimensional
changes (∆l). RPU/PIR foams tested here by thermostating at 120 ◦ C in dryer with forced circulation
during 48 hours caused slight changes of ∆l, ∆V, and ∆m (Table 5). Standards in civil engineering allow
for changes of 3% (for ∆V) and 1% (for ∆l) [39]. Measurements of linear dimensions, volume, and mass
were also made for foams degraded in the climatic chamber for one week (series 1t). Measurements of
the linear dimension, volume and mass do not indicate changes for the 1t series in relation to the 0t
series foams and were within the measurement error of ± 0.001%). The addition of cinnamon extract
and the presence or absence of flame retardant in foams did not affect the ∆l, ∆V, and ∆m values of
obtained foams.

Table 5. Results of foam aging measurement in an air dryer (120 ◦ C, 48 h).

Foam ∆l (%) ∆V (%) ∆m (%)

W +0.39 ± 0.00 −1.07 ± 0.01 2.27 ± 0.01
C5 +0.00 ± 0.00 −1.37 ± 0.01 2.09 ± 0.01
C10 +0.80 ± 0.00 −1.94 ± 0.01 2.35 ± 0.01
C15 +0.99 ± 0.00 −2.07 ± 0.01 2.91 ± 0.01
WU +0.21 ± 0.00 −1.89 ± 0.01 2.40 ± 0.01
CU5 +0.50 ± 0.00 −2.28 ± 0.01 2.31 ± 0.01
CU10 +0.95 ± 0.00 −2.41 ± 0.01 1.70 ± 0.01
CU15 +0.85 ± 0.00 −2.85 ± 0.01 1.42 ± 0.01

3.5. Compressive Strength

The literature [15,35] states that the assessment of the results of aging tests can be made by
specifying the compressive strength ratio (CV) in relation to the aging. CV in aging was calculated
as a ratio of compressive strength of 0t and 1t foams (Table 6). The choice of this property for the
assessment of aging was made due to its importance in the application of PUFs in civil engineering.
Appl. Sci. 2019, 9, 2663 13 of 23

A significant decreasing in compressive strength was observed for aged reference foams (W_1t and
WU_1t) in relation to the compressive strength of non-aged foams (W_0t and WU_0t). Therefore, these
foams had the lowest CV. Only the addition of cinnamon extract increased the value of the CV. This
could be related to the cross-linking formation in the foam structure due to the polyphenols present in
the cinnamon composition. However, more cinnamon-based filler content in the foam (both for the
series with flame retardant C and for the series without flame retardant CU) decreased this coefficient
by about 10%.

Table 6. Compressive strength (CS) and compressive strength ratio (CV): CS_0t—measured before
condition; CS_1t—measured after one-week condition.

CS_0t CS_1t CV
Foam
(kPa) (kPa) (%)
W 251.6 ± 6 140.5 ± 4 74.7 ± 2
WU 361.4 ± 9 256.2 ± 6 70.9 ± 2
C5 212.7 ± 6 200.1 ± 5 94.1 ± 2
C10 160.4 ± 4 143.9 ± 4 89.7 ± 2
C15 147.3 ± 3 126.6 ± 4 86.0 ± 2
CU5 121.4 ± 3 151.1 ± 4 124.4 ± 3
CU10 109.4 ± 2 132.8 ± 4 121.4 ± 3
CU15 91.9 ± 2 109.6 ± 3 119.2 ± 3

The CV ratio exceeded 100% for CU series foams. This meant that the strength of the aged
(CU_1t) foams increased in relation to the strength of non-aged foams (CU_0t). In the course of
photodegradation (apart from the destruction processes), there were also crosslinking and oxidizing.
FTIR studies were shown that the –CH bonds were destroyed (Figure 3). Free radicals could be formed
in the CU series, which were not blocked due to the lack of flame retardant (Antiblaze TMCP) as a
radical inactivator. The structure could probably was crosslinked. It led to a reinforcement of the foam
structure, thus increasing compressive strength [3].

3.6. FTIR Analysis

Susceptibility to degradation depends on the presence of specific chemical groups in the molecule.
The easily hydrolysable ester, amide, and urea groups accelerate the polymer decomposition [39,40].
Since photodegradation of polymeric materials takes place most intensively in the surface layer, up
to approx. 10 µm [41], the surface of degraded foams was scraped (1t series) and FTIR spectra of 1t
foams were compared with the 0t series spectra (not subjected to degradation). On the basis of the
FTIR analysis (Figure 4a,b), the following groups (Table 7) can be distinguished in the construction of
all foams: N–H, CH, –N=C=O, –N=C=N, C=O in urethane, isocyanurate, –C=N in the trimer, and
C–O. The polyurethane-polyisocyanurate structure of the obtained foams has been confirmed [1,5,8].

Table 7. Results of the FTIR analysis.

Band, cm−1 Bond

3325 N–H
2930 C-H
2276 –N=C=O
2137 –N=C=N–
1713 –C=O in urethane bond
1596 N–H
1512 N–H
1411 Isocyanurate ring
1225 C=N in trimer
1076 C–O
447 after degradation the intensity of bands related to bonds: CH (2930 cm–1), –N=C=O (2276 cm–1), –
448 N=C=N– (2137 cm–1), –C=O (1713 cm–1), –NH (1596 cm–1), –NH (1512 cm–1), isocyanuric (1411 cm–1), –
449 C=N in the trimer (1225 cm–1) and –C–OH (1076 cm–1) decreases after degradation (green line). Only
450 the band associated with the –OH (3325 cm–1) groups did not change (grey line).
451 Appl. Sci.Antioxidant
2019, 9, 2663 properties of flavonoids were determined by the presence of hydroxyl groups14in
of 23
452 both rings, the isomeria of their location, and the presence of a double bond and a carbonyl group in
453

454 Appl. Sci. 2019, 9, x 15 of 23

455 (a)
456

457
458 (b)
459 Figure4.4.FTIR
Figure FTIRof:
of:(a)
(a) C15_0t
C15_0t and
and C15_1t;
C15_1t; and
and(b)
(b)CU15_0t
CU15_0tand
andCU15_1t.
CU15_1t.

460 3.7.The FTIR(d),

Density spectra
Water(Figure 4a)(WA),
Absorption of theAbsorbability
foams with(A),
a maximum cinnamon
Softening Point extract content
(SP), Brittleness (B), and(15 wt%)
461 and
Content of Closed
with flame Cells (CC)
retardant content, before degradation (C15_0t) and after degradation (C15_1t) where
462 compared.The The FTIR density
apparent spectra of
of the
the foam
foam affects
with flame retardant properties.
its mechanical (C15_0t series)The subjected to degradation
main advantage of PU
463 (C15_1t)
materials, which are used in civil engineering, is their low density (and also good durability)bonds
showed that after degradation the intensity of the bands associated with the (red
[3]. The
−1 ), CH (2930 cm−1 ), –N=C=O (2276 cm−1 ), –C=O (1713 cm−1 ), –NH
464 lines) increases: N–H (3325 cm
decrease in foam density is also economically advantageous. The results of research on foams
465 (1596 cm−1 ),by
modified –N–H (1512 cm
cinnamon
−1 ), isocyanurate ring (1411 cm−1 ), –C=N in the trimer (1225 cm−1 ), –C–OH
extract (Table 8) showed that the apparent density of C_0t foams decreased
−1 cm−1
466 (1076
fromcm39.67). The
kg/m bond associated
3 (W_0t) to 33.97with the
kg/m –N=C=N–
3 (C15_0t). For(2137
a series green line)
of, foams decreased.
without commercial flame
467 retardant –FR (CU_0t), density slightly decreased from 30.94 kg/m (CU5_0t) content
The figure (Figure 4b) compares the foams with a maximum cinnamon 3 extract to 29.43(15%
kg/mwt.),
3

468 without flameThe

(CU15_0t). retardant
densitybefore
of thedegradation
reference foam(CU15_0t) and after
WU_0t was degradation
49.6 kg/m 3 (CU15_1t).
. The reason for theThe spectra
decrease in of
469 foam density was most probably the incorporation of cinnamon compounds (e.g., flavonoids,
470 chlorogenic acids, phenol acids and others) into the structure [42–44]. They have contributed to the
471 opening of foam cells and thus the decrease of density, which resulted in a decrease in brittleness
472 (Table 8) and compressive strength (Table 6). FR was embedded in the structure of the C foam series
473 and thereby reduced their brittleness compared to the brittleness of the CU foam series.to the foam
Appl. Sci. 2019, 9, 2663 15 of 23

FTIR foams without flame retardant (CU_0t series) subjected to degradation (CU_1t) showed that after
degradation the intensity of bands related to bonds: CH (2930 cm−1 ), –N=C=O (2276 cm−1 ), –N=C=N–
(2137 cm−1 ), –C=O (1713 cm−1 ), –NH (1596 cm−1 ), –NH (1512 cm−1 ), isocyanuric (1411 cm−1 ), –C=N in
the trimer (1225 cm−1 ) and –C–OH (1076 cm−1 ) decreases after degradation (green line). Only the band
associated with the –OH (3325 cm−1 ) groups did not change (grey line).
Antioxidant properties of flavonoids were determined by the presence of hydroxyl groups in both
rings, the isomeria of their location, and the presence of a double bond and a carbonyl group in the
heterocyclic ring [42]. Bands whose intensity increased were prone to degradation.

3.7. Density (d), Water Absorption (WA), Absorbability (A), Softening Point (SP), Brittleness (B), and Content
of Closed Cells (CC)
The apparent density of the foam affects its mechanical properties. The main advantage of PU
materials, which are used in civil engineering, is their low density (and also good durability) [3].
The decrease in foam density is also economically advantageous. The results of research on foams
modified by cinnamon extract (Table 8) showed that the apparent density of C_0t foams decreased
from 39.67 kg/m3 (W_0t) to 33.97 kg/m3 (C15_0t). For a series of foams without commercial flame
retardant –FR (CU_0t), density slightly decreased from 30.94 kg/m3 (CU5_0t) to 29.43 kg/m3 (CU15_0t).
The density of the reference foam WU_0t was 49.6 kg/m3 . The reason for the decrease in foam density
was most probably the incorporation of cinnamon compounds (e.g., flavonoids, chlorogenic acids,
phenol acids and others) into the structure [42–44]. They have contributed to the opening of foam cells
and thus the decrease of density, which resulted in a decrease in brittleness (Table 8) and compressive
strength (Table 6). FR was embedded in the structure of the C foam series and thereby reduced their
brittleness compared to the brittleness of the CU foam series.to the foam causes a decrease in the
softening point of modified foams by 18 ◦ C in the C_0t series and 32 ◦ C in the CU t series. The amount
of cinnamon extract in the C_0t series foams practically did not affect the brittleness of foams, whereas
for the CU_0t foams series, the CU_0t foam brittleness increase was observed in relation to the WU_0t
foam, but its decrease with the increase of cinnamon-based filler content in the foam was observed; see
Table 8. The reason for the CU_0t brittleness increase (in relation to for the CU_0t series) was lack of
flame retardant in foams.

Table 8. Absorbability (A), water absorption (WA), softening point (SP), brittleness (B), apparent
density (d), and content of closed cells (CC).

Foam A (%) WA (%) SP (◦ C) B (%) d (kg/m3 ) CC (%)

W 12.33 ± 0.37 5.15 ± 0.05 184 ± 5 13.27 ± 0.01 39.67 ± 0.03 83.2 ± 0.2
C5 13.41 ± 0.40 5.67 ± 0.06 189 ± 6 14.34 ± 0.01 39.60 ± 0.03 74.3 ± 0.2
C10 22.34 ± 0.67 6.14 ± 0.06 181 ± 5 13.04 ± 0.01 35.72 ± 0.02 39.1 ± 0.1
C15 36.05 ± 1.08 9.64 ± 0.10 166 ± 5 11.93 ± 0.01 33.97 ± 0.02 5.7 ± 0.0
WU 8.14 ± 0.04 3.12 ± 0.01 204 ± 6 16.42 ± 0.01 49.60 ± 0.03 89.5 ± 0.3
CU5 23.22 ± 0.69 3.78 ± 0.01 185 ± 6 45.60 ± 0.31 30.94 ± 0.02 17.4 ± 0.5
CU10 18.04 ± 0.54 4.02 ± 0.01 179 ± 6 44.22 ± 0.31 29.19 ± 0.02 23.4 ± 0.7
CU15 17.14 ± 0.51 4.99 ± 0.02 172 ± 6 42.13 ± 0.29 29.43 ± 0.02 28.1 ± 0.8

There are many factors that determine the type of insulation and its thickness. For the insulation
to be fully effective, it should meet at least the basic requirements, which include low absorbability and
low water absorption from the environment [36]. Reduction of this parameters is very beneficial when
these materials are using as thermal insulation. A lack of ability for water to accumulate in foams
prevents a multiplication of mold and other microorganisms in the rooms where they are used [7,8,37].
In the investigated foams, an increase of water absorption (WA), absorbability (A) was observed
with an increasing content of cinnamon extract in foams (Table 8). The increase in WA and W is
due to the hydrophilic nature of the filler (cinnamon), which contains, among others, polyphenols
(chlorogenic acid, flavonoids, and phenol acids); see Table 1. These compounds have hydrophilic –OH
492 and –COOH bonds (about 1077 cm–1 and 2928 cm–1). The unidentified residue was most likely
493 cellulose with –OH groups. The increase in A and WA was also caused by the opening of cells after
494 the addition of cinnamon extract to the foams; see Table 8. Increase in absorbability (A) and water
495 absorption (WA), was also observed for foams modified with ground coffee [45]. Opening of the cells
496 Appl.
wasSci.confirmed
2019, 9, 2663by the SEM method (Figure 5c,f). The increase in brittleness (B) in CU_0t foams (about 16 of 23

497 42%–45%) was caused by the lack of flame retardant. Antiblaze was embedded between the walls of
498 the C_0t series foams and stiffened the structure by gluing it together. Its absence caused a decrease
and –COOH groups. The presence of these groups was confirmed by the FTIR analysis (Figure 3).
499 in the stiffening of the foam structure and thus increased brittleness.
This analysis revealed the presence of a wide –OH band in the wave region of about 3346 cm−1 ) and
500 The addition of cinnamon clearly affects the opening of the foam cells. This causes an increase
–COOH bonds (about 1077 cm−1 and 2928 cm−1 ). The unidentified residue was most likely cellulose
501 in absorptivity (A). Both closed-cell and open-cell foams show suitability in insulation [25,36]. If the
with –OH groups. The increase in A and WA was also caused by the opening of cells after the addition
502 increase in the volume of bubbles (and reducing the thickness of their walls) is not strictly
503 of cinnamon
synchronized extract
withtothetheincrease
foams; see Table
in the 8. Increase
viscosity of theinmixture,
absorbability (A)escapes
the gas and water absorption
to the (WA),
outside. The
504 was also observed
opening for foams
of cells during the modified withprobably
synthesis was ground coffee [45]. by
influenced Opening of the cells
the elongation was
of free confirmed
rise time andby
505 thestring
SEM gel method (Figure 5c,f). The increase in brittleness (B) in CU_0t foams (about
time (Table 3). The CO2 formed in the cells caused the cell to break before it gelled. The 42%–45%) was
506 caused
opening by the lack
of the of flame
foam retardant.
cells was Antiblaze
influenced was embedded
by an increase between
in the heat thecoefficient
transfer walls of the C_0t series
λ, which for
507 foams and stiffened
all foams ranged from the structure by gluing
0.0353 W/(m∙K) it together.
to 0.0356 W/(m∙K). Its For
absence caused
standard a decrease
foams W_0t and in WU_0t
the stiffening
was
508 of the
0.026foam structure
W/(m∙K). Open and
cellthus
foamincreased
has lowerbrittleness.
strength than closed cell [36]; see Table 6.
509

(a) (b)

Appl. Sci. 2019, 9, x (c) (d) 17 of 23

(e) (f)
510 Figure
Figure 5. 5.
SEMSEM micrographsofoffoams:
micrographs foams: (a)
(a) W_0t,
W_0t, (b)
(b) W_1t;
W_1t;(c)
(c)C15_0t;
C15_0t;(d)
(d)C15_1t;
C15_1t;(e)(e)
CU15_0t; and
CU15_0t; (f) (f)
and
511 CU15_1t.
CU15_1t.

512 Table 8. Absorbability (A), water absorption (WA), softening point (SP), brittleness (B), apparent
513 density (d), and content of closed cells (CC).

Foam A (%) WA (%) SP (°C) B (%) d (kg/m3) CC (%)

W 12.33 ± 0.37 5.15 ± 0.05 184 ± 5 13.27 ± 0.01 39.67 ± 0.03 83.2 ± 0.2
C5 13.41 ± 0.40 5.67 ± 0.06 189 ± 6 14.34 ± 0.01 39.60 ± 0.03 74.3 ± 0.2
Appl. Sci. 2019, 9, 2663 17 of 23

The addition of cinnamon clearly affects the opening of the foam cells. This causes an increase
in absorptivity (A). Both closed-cell and open-cell foams show suitability in insulation [25,36]. If the
increase in the volume of bubbles (and reducing the thickness of their walls) is not strictly synchronized
with the increase in the viscosity of the mixture, the gas escapes to the outside. The opening of cells
during the synthesis was probably influenced by the elongation of free rise time and string gel time
(Table 3). The CO2 formed in the cells caused the cell to break before it gelled. The opening of the foam
cells was influenced by an increase in the heat transfer coefficient λ, which for all foams ranged from
0.0353 W/(m·K) to 0.0356 W/(m·K). For standard foams W_0t and WU_0t was 0.026 W/(m·K). Open cell
foam has lower strength than closed cell [36]; see Table 6.

3.8. Flame Properties

Foam flammability research showed synergy between Antiblaze TCMP and cinnamon extract.
When conducting flammability tests on foams without flame retardants and with cinnamon-based filler
(CU_0t series), was observed the increase of limited oxygen index (LOI) compared to the reference
foam WU_0t (Table 9). LOI was increased from 18.7% (WU_0t) to 21% (CU15_0t). In foams without
flame retardant, but with cinnamon extract, there were any changes in the LOI of the C_0t series
(with cinnamon extract) to the W_0t foam and it was about 24% for the C_0t series and the W_0t
foam. A two-fold increase in combustion residues (CR) from 37.72% (WU_0t) to 64.98% (CU5_0t) was
observed in a series of non-flame-retarding foams (WU_0t, CU_0t). Combustion residue foams with
cinnamon-based filler and flame retardant (series C_0t) increased by about 10% compared to the foam
without biofiller (W_0t). For a series that did not contain a flame retardant (CU_0t), the CR value
increased by approximately 30% in relation to the retention of the reference foam WU_0t. Between the
reference foams W_0t and WU_0t, a 40% increase in retention for the W_0t foam (containing Antiblaze
TMCP) was observed in relation to the retention of the WU_0t foam. The decrease in flammability was
probably influenced by the composition of cinnamon (Table 1) and in particular the content of heavy
metals (in ppm). In horizontal tests all foams were classified as self-extinguishing.

Table 9. Flame properties of foams: combustion residue (CR); limited oxygen index (LOI); and
horizontal test (HT).

Foam CR (%) LOI (%vol. of O2 ) HT

W 83.4 ± 1.6 24.7 ± 0.2
C5 91.2 ± 1.8 24.4 ± 0.2
C10 91.6 ± 1.8 24.6 ± 0.2
C15 91.7 ± 1.8 23.7 ± 0.2 self-extinguishing
WU 37.7 ± 0.8 18.5 ± 0.1
CU5 650 ± 0.9 21.0 ± 0.2
CU10 63.3 ± 0.9 20.3 ± 0.1
CU15 63.3 ± 0.9 20.2 ± 0.1

3.9. Differential Scanning Calorimetry

The DSC curves recorded effects, such as: the temperature of the beginning of the thermal effect
(Toneset ), the temperature of the end of the thermal effect (Tk ), the temperature of the extreme point
(Tmax ), and enthalpy (H) [46].
The DSC graph of cinnamon-filled foams (series C_0t) containing a flame retardant in the
composition has one endothermic peak P1 and two and exothermic peaks P2 and P3 (Figure 6a,b). The
absence of flame retardant in foams (series CU_0t) results in a change in the course of the DSC curves
(Figure 6c,d). We could observe two endothermic peaks P1 and P2 and one exothermic P3 in the figure.
From the graphs (Figure 6), it can be observed that the increasing amount of cinnamon extract
(from 5% by weight to 15% by weight) increases the enthalpy H1 in the first endothermic peak
(Figure 6a) from 26.47 J/g (C5_0t) to 36.53 J/g (C15_0t); see Table 10. Enthalpy H1 was associated
Appl. Sci. 2019, 9, 2663 18 of 23

with the evaporation of water from foams. Its increase was caused by the increasing content of the
biofiller in the foams. H1 for the foam without cinnamon extract (W_0t) was 25.75 J/g. The maximum
temperature (Tmax in P1) also increased from 71.8 J/g (W_0t) to 85.6 J/g (C15_0t). There was a reduction
in the intensity (size) of the first exothermic peak (P2) associated with the decomposition of urethane
bonds and ether bonds from polyol at Tmax2 around 295 ◦ C (for W_0t foam) and its goes towards a
lower temperature, i.e., 270 ◦ C for C15_0t foam). The Tmax3 of the second exothermic peak (P3) was
practically unchanged. The curves of CU_1t foams series (Figure 4b) degraded one week were similar
Appl. Sci. 2019, 9, x 18 of 23
to C_0t series. However, the H2 and H3 enthalpy values or P2 and P3 peaks were smaller.

(a) (b)

(c) (d)
Figure
Figure 6.
6. DSC
DSCcurves
curves of
of foams
foams modified
modified by
by cinnamon
cinnamon extract:
extract: (a)
(a) C_0t
C_0t series;
series; (b)
(b) series
series C_1t;
C_1t; (c)
(c) series
series
CU_0t;
CU_0t; and (d) series CU_1t.

From the graphs (Figure 6), it can be observed that the increasing amount of cinnamon extract
Table 10. Values of thermal transformations of foams series C (with flame retardant) using the DSC.
(from 5% by weight to 15% by weight) increases the enthalpy H1 in the first endothermic peak (Figure
0t—foams before degradation, 1t—foams after 1-week degradation.
6a) from 26.47 J/g (C5_0t) to 36.53 J/g (C15_0t); see Table 10. Enthalpy H1 was associated with the
evaporation of water from
Peak P1foams. Its increase was caused Peak P2 by the increasing content of the
Peak P3 biofiller in
the foams.
Foam H 1 for
Tonset , Tmax1 the foam
Tk1 without
H1 cinnamon
Tonset2 Tmax2 extract
Tk2 (W_0t)
H2 was 25.75 J/g.
Tonset3 Tmax3 The Tk3maximum
H3
temperature(◦ C)(Tmax(in
◦ C) (◦ C)increased
P1) also (◦ C)71.8 J/g
(J/g) from (◦ C)(W_0t)
(◦ C)
to 85.6 (◦ C) There
J/g (C15_0t).
(J/g) (◦ C) was (◦ C)
a reduction
(J/g)
inW_0t
the intensity
21.7 (size)
71.8 of the first exothermic
146.6 25.8 peak294.8
278.6 (P2) associated
325.3 with the
44.9 decomposition
326.3 330.4 of urethane
347.3 5.1
bonds
C5_0t and44.6
ether bonds
82.3 from 131.4 polyol
26.5 at T266.0
max2 around
285.9 295316.6
°C (for28.0
W_0t foam)
330.2 and its goes
335.9 351.6towards
4.6 a
C10_0t
lower 46.7
temperature, 86.4 139.4
i.e., 270 °C for33.4
C15_0t261.9
foam).274.5
The T319.1 35.6 324.0 329.8 352.7
max3 of the second exothermic peak (P3) was
6.1
C15_0t 46.7 85.6 140.8 36.5 262.6 271.0 314.4 30.8 327.1 333.2 357.7 8.9
practically unchanged. The curves of CU_1t foams series (Figure 4b) degraded one week were similar
W_1t 54.7 91.3 179.8 41.8 271.5 289.0 314.4 19.0 318.2 323.6 342.2 4.7
toC5_1t
C_0t series.
39.7 However,
93.9 the H2 and
133.9 47.5H3 enthalpy
259.7 values 313.0
285.3 or P2 and P3 peaks
13.8 331.2were smaller.
337.5 358.8 5.2
Subjecting
C10_1t 40.1 the foams140.0
94.0 (CU_1t50.0series)249.7
to a 1-week
271.2 degradation
310.4 was shown
15.5 329.6 of334.1
the Tmax peaks going
342.5 7.1
C15_1t higher
towards 47.4 temperatures,
94.4 142.2 e.g.,
53.0
for P1244.8 267.3 81.2
peak from 305.8 17.8
°C (CU15_0t) 323.0
to 91.0333.4 363.2 for
°C (CU15_1t), 11.1P2
peak with 282.3 °C (CU15_0t) up to 325.2 °C (CU15_1t) in Table 11.
Degradation of the reference foam WU_0t (without cinnamon extract, without flame retardant)
resulted in the disappearance of the endothermic peak of the WU_1t foam (Figure 6c,d). In the CU_1t
foam series (Figure 5d), pronounced endothermic peaks were observed at temperatures above 300 °C
for CU5_1t, CU10_1t, CU15_1t foams. Any endothermic peak was not observed for WU_1t, at
Appl. Sci. 2019, 9, 2663 19 of 23

Subjecting the foams (CU_1t series) to a 1-week degradation was shown of the Tmax peaks going
towards higher temperatures, e.g., for P1 peak from 81.2 ◦ C (CU15_0t) to 91.0 ◦ C (CU15_1t), for P2
peak with 282.3 ◦ C (CU15_0t) up to 325.2 ◦ C (CU15_1t) in Table 11.

Table 11. Values of thermal transformations of foams series CU (without flame retardant) by using the
DSC. 0t—foams before degradation, 1t—foams after one week degradation.

Peak P1 Peak P2 Peak P3

Foam Tonset1 Tmax1 Tk1 H1 Tonset2 Tmax2 Tk2 H2 Tonset 3 Tmax3 Tk3 H3
(◦ C) (◦ C) (◦ C) (J/g) (◦ C) (◦ C) (◦ C) (J/g) (◦ C) (◦ C) (◦ C) (J/g)
WU_0t s 29.6 78.1 129.6 33.1 227.8 325.6 354.0 76.6 354.0 374.7 391.6 5.71
CU1_0t 47.6 81.2 121.8 14.2 213.5 261.3 322.0 93.7 327.9 356.7 392.3 37.1
CU5_0t 37.1 82.5 129.6 27.4 219.3 279.6 315.3 136.7 315.3 348.7 394.2 46.1
CU15_0t 35.6 84.1 138.0 55.0 221.3 282.3 320.0 116.0 307.1 336.2 395.1 10.1
WU_1t 54.7 91.1 179.8 41.6 271.5 289.0 314.4 19.0 318.2 323.6 342.2 4.4
CU1_1t 37.8 82.8 136.1 49.6 221.3 308.1 326.9 147.6 326.9 352.0 391.6 36.8
CU5_1t 35.6 84.1 141.4 54.9 218.6 287.3 320.0 146.0 320.0 346.3 386.2 20.6
CU15_1t 38.3 91.0 150.9 82.9 279.9 325.2 355.8 49.2 354.7 368.7 390.5 4.0

Degradation of the reference foam WU_0t (without cinnamon extract, without flame retardant)
resulted in the disappearance of the endothermic peak of the WU_1t foam (Figure 6c,d). In the
CU_1t foam series (Figure 5d), pronounced endothermic peaks were observed at temperatures above
300 ◦ C for CU5_1t, CU10_1t, CU15_1t foams. Any endothermic peak was not observed for WU_1t, at
approximately 300 ◦ C. The disappearance of the first exothermic P2 peak was also observed in the
temperature range from 265 ◦ C to 300 ◦ C (occurring in the C_0t and C_1t series containing the flame
retardants; Figure 6a,b) relative to the series without flame retardant (CU_0t and CU_1t, Figure 6c,d).
The second exothermic peak P3, was preserved.
The changes in the peaks observed in Figure 6c,d could indicate the breakdown of urethane bonds
(with dissociation temperature of 200 ◦ C) and ether (with dissociation temperature of 260 ◦ C) [47–50].
The presence of the P3 peak on the DSC curve suggested the lack of climatic influence on the PUR/PIR
foam degradation (with dissociation temperature of 350 ◦ C) in CU_1 series, what could be observed on
FTIR of CU_1t series of foams; see Figure 4b.

3.10. RPU/PIR Foam Structure

Foam structure was analyzed by using SEM. The density of foams affected on the thickness of
the cell walls (and thus the strength of the foams) [50,51]. The structure of foams with cells smaller
than 0.25 mm in diameter is referred to as small cells [42]. Cells with a diameter above 0.5 mm are
referred to as large. The small-cell structure gives porous materials more favorable mechanical strength.
In flexible foams, a decrease in the diameter of the foam cells was observed after the addition of flame
retardant halogen-free organophosphorus compound (Fyrol PNX) [52].
The addition of cinnamon extract caused a slight decrease in density of these foams (Table 8). This
could affect the opening of modified foam cells. A specialized program for measuring cells in the SEM
method allowed the measurement of foam cell width and length. Based on the width and height of the
cells, the anisotropy coefficient was calculated according to Equation (13).

height cells
Anisotropy coe f f icient = (13)
width cells
The anisotropy factor > 1 means the elongation of cells in the vertical direction. The highest strength
parameters are characterized by foams with anisotropy coefficient equal to 1 (not elongated neither
vertically nor horizontally) [27]. The anisotropy of analyzed foams was about 1.
The cell walls were destroyed during conditioning (Figure 5b,d,f) (under given conditions) and
additional holes were formed. In the SEM study, these additional holes were interpreted and measured
by the program as cells (and not as holes created as a result of wall destruction). On a given surface (in
Appl. Sci. 2019, 9, 2663 20 of 23

this case 1 mm2 ) additional holes were interpreted as a smaller cells (not as a real cells). In fact, the
results in Table 12 relate to measurements of holes created after destruction and not measurements
of real cells. Measurements proved that foams conditioning (series 1t) were destroyed (the thinnest
fragments of the walls were broken); see Figure 5b,d,f).

Table 12. Results of SEM micrograph analysis.

Cell/Hole Content of Cell/Hole

Cell/Hole Cell/Hole Anisotropy
Foam Symbol Surface Area per Area Unit
Height (µm) Width (µm) Coefficient
(mm2 ) (cell/mm2 )
W_0t 606.6 ± 2 540.7 ± 2 1.12 ± 0.00 0.258 ± 0.001 3.88 ± 0.01
C5_0t 399.0 ± 1 326.4 ± 1 1.22 ± 0.00 0.102 ± 0.001 9.80 ± 0.01
C15_0t 325.3 ± 1 322.4 ± 1 1.01 ± 0.00 0.084 ± 0.001 11.92 ± 0.03
W_1t 367.7 ± 1 340.9 ± 1 1.08 ± 0.00 0.098 ± 0.001 10.20 ± 0.03
C5_1t 359.7 ± 2 348.1 ± 1 1.05 ± 0.00 0.085 ± 0.001 11.77 ± 0.03
C15_1t 260.4 ± 2 249.0 ± 2 1.04 ± 0.00 0.051 ± 0.001 19.69 ± 0.04
CU5_0t 598.4 ± 2 613.0 ± 2 0.98 ± 0.00 0.288 ± 0.001 3.47 ± 0.01
CU15_0t 563.8 ± 2 558.2 ± 2 0.97 ± 0.00 0.255 ± 0.001 3.52 ± 0.01
CU5_1t 981.1 ± 2 978.2 ± 2 1.00 ± 0.00 0.754 ± 0.001 1.33 ± 0.00
CU15_1t 980.3 ± 2 916.4 ± 2 1.06 ± 0.00 0.705 ± 0.001 1.42 ± 0.00

Based on results in Table 12, it was read that cinnamon extract increased the destruction of foams.
It was evidenced by the increased number of holes per 1 mm2 of surface. The number of holes (“cells”)
of conditioned foams of C series (containing flame retardant) increased according to increasing content
of cinnamon extract in foams (Table 12) from 3.8 (W_1t) to 19.69 cell/mm2 (W15_1t).
Considering foams without flame retardant (CU series), content of cells per mm2 decreased twice
after condition. It means that not only walls of foam were destructed, but even ribs were cracked
and, thus, cells were opened. Number of holes (cells) per 1 mm2 decreased from about 3.5 cell/mm2
(CU5_1t and CU15_1t) to about 1.5 cell/mm2 (WU5_1t and WU15_1t).

4. Conclusions
Two series of foams with cinnamon extract were obtained: one with flame retardant (C_0t) and
the other without flame retardant (CU_0t). The results of this research showed an improvement of
some properties of foams with biofiller. The measurement of the color indicates an increase in the
red color of foams subjected to conditioning (accelerated degradation conditions) and an increase in
the color of blue in thermostated foams (for 48 hours in an exhaust dryer). In cinnamon-modified
RPU/PIR foams with and without flame retardants was observed decrease in compressive strength
from 251.63 kPa (W_0t foam) to 147.29 kPa (C15_0t foam) and from 361.39 kPa (WU_0t) to 91.93 kPa
(CU15_0t). The observed decrease of brittleness was from 13% to 11% (in C series) and an increase from
16% to 45% in CU series of foams. In addition, increasing amount of cinnamon extract in the C series
(from 5% to 15%) increased the H1 enthalpy at a temperature of about 80 ◦ C–95 ◦ C (from 25.75 J/g,
W0t to 36.53 J/g, C15_0t, and to 54.94 J/g, CU15_0t). The oxygen index was between 18.5% and 20.2%
(C series) and between 23.7% and 24.7% (CU series). The combustion residue (CR) after the burning of
foams containing cinnamon extract and flame retardant (series C_0t) increased by about 10% in relation
to the foam without biofiller (W_0t). For a series without flame retardant (CU_0t), the CR increased by
about 30% in relation to the CR of the reference foam WU_0t. The difference in CR between reference
foams W_0t and WU_0t was about 40%. W_0t foam, containing Antiblaze TMCP, had a CR of 83.44
and WU_0t was 37.72%. The addition of cinnamon extract contributed to increasing the foams’ CR
to 91.68% for C15_0t and to 63.33% for CU15_0t. Cinnamon-based filler showed synergism with
Antiblaze TMCP in reducing flammability. Foams containing flame retardant and cinnamon extract
(C_0t series) were characterized by the highest combustion residue. Conditioning caused decrease
in compressive strength for C_1t series of foam by about 20 kPa (in comparison to the C_0t series).
Destruction of characteristic bonds (e.g., cracking urethane bond) occurred was a result of a combined
effect of temperature, humidity, and UV radiation in the conditioner.
Appl. Sci. 2019, 9, 2663 21 of 23

Author Contributions: Conceptualization: J.L; methodology: J.L., M.I., and K.M.; software: J.L.; validation: J.L.;
formal analysis: J.L. and M.B.; investigation, J.L.; data curation: J.L.; writing—original draft preparation: J.L.;
visualization: J.L.; supervision: J.P.-S. and B.C.
Funding: An article fined in fifty percent of the grant National Science Center (NCN) no. 2015/17/DST8/02618
(K. Moraczewski).
Conflicts of Interest: The authors declare no conflict of interest.

References
1. Czupryński, B. Issues in Chemistry and Technology of Polyurethanes; WN AB: Bydgoszcz, Poland, 2004.
2. Żabski, L. PIR foams—A new type of insulation: Rigid polyurethane foam. Mater. Bud. 2005, 1, 46–47.
3. Żuchowska, D. Construction Polymers; WNT: Warsaw, Poland, 2000.
4. Randall, D.; Lee, S. (Eds.) The Polyurethanes Book; Wiley LTD.: New York, NY, USA, 2002.
5. Prociak, A.; Pielichowski, J. Characteristics of rigid polyurethane boilings in the aspect of new porophors
application. Czas. Tech. 1998, R95, 26–52.
6. Polyurethane Foam Composition. Available online: https://patents.google.com/patent/US6894083B2/en
(accessed on 26 June 2019).
7. Paciorek-Sadowska, J.; Borowicz, M.; Czupryński, B.; Tomaszewska, E.; Liszkowska, J. Oenothera biennis
seed oil as an alternative raw material for production of bio-polyol for rigid polyurethane-polyisocyanurate
foams. Ind. Crop. Prod. 2018, 126, 208–217. [CrossRef]
8. Paciorek-Sadowska, J.; Borowicz, M.; Czupryński, B.; Isbrandt, M. Effect of Evening Primrose Oil-Based
Polyol on the Properties of Rigid Polyurethane–Polyisocyanurate Foams for Thermal Insulation. Polymers
2018, 10, 1334. [CrossRef] [PubMed]
9. Liszkowska, J.; Czupryński, B.; Paciorek-Sadowska, J.; Moraczewski, K. The effect of UV radiation on the
properties of PUR-PIR foam. Adv. Polym. Technol. 2015, 36, 21631–21639. [CrossRef]
10. Agrawal, A.; Kaura, R.; Walia, R.S. PU foam derived from renewable sources: Perspective on properties
enhancement: An overview. Eur. Polym. J. 2017, 95, 255–274. [CrossRef]
11. Soares, B.; Gama, N.; Freire, C.S.R.; Timmons, A.B.; Brandão, I.S.; Neto, C.P.; Ferreira, A. Spent coffee grounds
as a renewable source for ecopolyols production. J. Chem. Technol. Biotechnol. 2015, 90, 1480–1488. [CrossRef]
12. Levchik, S.V.; Weil, E.D. Thermal decomposition, combustion and fire-retardancy of polyurethanes-a review
of the recent literature. Polym. Int. 2004, 53, 1585–1610. [CrossRef]
13. G˛ebura, A.; Kowalska, D.; Tokarski, T. Research on Accelerated Aging of Electric Wires. Available online: http:
//www.academia.edu/17704721/Badania_przyśpieszonego_starzenia_przewodów_elektrycznych (accessed
on 1 December 2018).
14. Kolbiński, K.; Słowikowski, J. Materials Electricial; WNT: Warszawa, Poland, 1988.
15. Broniewski, T.; Kapko, J.; Płaczek, W.; Thomalla, J. Test Methods and Evaluation of Plastic Properties; WNT:
Warsaw, Poland, 2000.
16. Szumniak, J.; Smoczyński, Z.; Szcześniak, K. Armament and Military Equipment Polymer Composite Ageing;
Zeszyty Naukowe WSOWL: Wrocław, Poland, 2011; Volume 1, pp. 270–285.
17. Prociak, A.; Rokicki, G.; Ryszkowska, J. Polyurethane Materials; WN PWN: Warsaw, Poland, 2014.
18. Bajda, M.; Pogoda, M. Study of the effect of conveyor belt accelerated heat aging on its strength. Transport
2016, 1, 16–22.
19. Liszkowska, J. Citric acid used in the production of polyols for rigid PUR-PIR foams. Polym. Bull. 2017, 74,
283–305. [CrossRef]
20. Rytlewski, P.; Malinowski, R.; Moraczewski, K.; Żenkiewicz, M. Influence of some crosslinking agents on
thermal and mechanical properties of electron beam irradiated polylactide. Radiat. Phys. Chem. 2010, 79,
1052–1057. [CrossRef]
21. Gramza, A.; Korczak, J.; Amarowicz, R. Tea polyphenols—Their antioxidant properties and biological activity.
Pol. J. Food Nutr. Sci. A Rev. 2005, 55, 219–235.
22. Lee, L.W.; Cheong, M.W.; Curran, F.; Bin, Y.; Shao, Q.L. Coffee fermentation and flavor—An intricate and
delicate relationship. Food Chem. 2015, 185, 182–191. [CrossRef] [PubMed]
23. Kudła, S. Technological aspects of phenolic antioxidants interactions with dicumyl peroxide in the processes
of polyolefins’ crosslinking. Polimery 2005, 50, 43–47. [CrossRef]
Appl. Sci. 2019, 9, 2663 22 of 23

24. Półka, M. Analysis of the toxicity of thermal decomposition and combustion products obtained from selected
epoxy materials. Res. Dev. 2010, 19, 73–78.
25. Richard, C.; Thompson, R.C.; Moore, C.J.; Frederick, S.; vom Saal, F.S.; Swan, S.H. Plastics, the environment
and human health: current consensus and future trends. Philos. Trans. R Soc. Lond. B Biol. Sci. 2009, 364,
2153–2166.
26. Liszkowska, J.; Czupryński, B.; Paciorek-Sadowska, J.; Michałowski, S. Thermal and flammable properties of
rigid PUR–PIR foams obtained by using new compounds based on 2-hydroxypropane-1.2.3-tricarboxylic
acid. J. Cell. Plast. 2016, 52, 321–341. [CrossRef]
27. Liszkowska, J. Properties of Rigid PUR-PIR Foams Obtained with the Condensation of Citric Acid with Diols and
Selected Glycolysates; WU UKW: Bydgoszcz, Poland, 2016.
28. Technical Card of Cinnamon; Agrema Sp. z o.o: Wrocław, Poland.
29. Wirpsza, Z. Poliuretanes. Chemistry, Technology, Application; WNT: Warsaw, Poland, 1991.
30. Liszkowska, J.; Czupryński, B.; Paciorek-Sadowska, J. Thermal properties of polyurethane-polyisocyanurate
(PUR-PIR) foams modified with tris(5-hydroxypentyl)-2-hydroxypropane-1,2,3-tricarboxylate. J. Adv. Chem.
Eng. 2016, 6, 148–154. [CrossRef]
31. Czupryński, B.; Liszkowska, J.; Paciorek-Sadowska, J. Modification of rigid polyurethane-polyisocyanurate
foam selected powder fillers. Polimery 2008, 3, 48–52.
32. Mańczak, K. Experiment Planning Technique; WNT: Warszawa, Poland, 1976.
33. ASTM Standard D7487–13e1. Standard Practice for Polyurethane Raw Materials: Polyurethane Foam Cup Test;
ASTM International: West Conshohocken, PA, USA, 2016. [CrossRef]
34. Operating Instructions for the Climate Chamber Model CCK-40/300 NG, Es-tor.
35. Szczepaniak, W. Instrumental Methods in Chemical Analysis; PWN: Warsaw, Poland, 2011.
36. Prociak, A. High-Tech Insulation Polyurethane Materials; WU PK: Cracow, Poland, 2008.
37. Paciorek-Sadowska, J.; Borowicz, M.; Czupryński, B.; Liszkowska, J.; Tomaszewska, E. Application of
halloysite as filler in the production of rigid PUR-PIR foams. Polimery 2018, 63, 185–190. [CrossRef]
38. Gama, N.V.; Silva, R.; Mohseni, F.; Davarpanah, A.; Amaral, V.S.; Ferreira, A.; Barros-Timmons, A.
Enhancement of physical and reaction to fire properties of crude glicerol polyurethane foams filled with
expanded graphite. Polym. Test. 2018, 69, 199–207. [CrossRef]
39. Paciorek-Sadowska, J.; Borowicz, M.; Czupryński, B.; Liszkowska, J. Composites of rigid
polyurethane-polyisocyanurate foams with oak bark. Polimery 2017, 62, 666–672. [CrossRef]
40. Rojek, M. Methodology of Diagnostic Tests of Layered Composite Materials with a Polymer Matrix (in Polish).
Open Access Libr. 2011, 2, 11–31.
41. Paczkowski,
˛ J. Photochemistry of Polymers. Theory and Applications; WU UMK: Toruń, Poland, 2003.
42. Czaplińska, M.; Czepas, J.; Gwoździński, K. Structure, antioxidant and anti-cancer properties flavonoid bike.
Adv. Biochem. 2012, 58, 235–244.
43. Yi-Fang, C. (Ed.) Coffee: Emerging Health Effects and Disease Prevention; John Wiley & Sons, Inc.: New York,
NY, USA; Blackwell Publishing Ltd.: Oxford, UK, 2012.
44. Gawlik-Dziki, U. Phenolacids as bioactive food ingredients. Food Sci. Technol. Qual. 2004, 4, 29–40.
45. Liszkowska, J. The effect of ground coffee on the mechanical and application properties of rigid
polyurethane-polyisocyanurate foams. Polimery 2018, 63, 305–310. [CrossRef]
46. Liszkowska, J.; Paciorek-Sadowska, J.; Czupryński, B. Temperature stability and thermal properties of
polyurethane-polyisocyanurate foams obtained using products of citric acid condensation. Polimery 2018, 63,
503–514. [CrossRef]
47. Czupryński, B.; Paciorek-Sadowska, J.; Liszkowska, J. Heat and thermal reistance of rigid
polyurethane-polyisocyanurate foams with addition of polyethylene, polypropylene and foamed polystyrene
recyclates. Inżynieria I Apar. Chem. 2008, 4, 15–16.
48. Paciorek-Sadowska, J. Research on the Influence of Boric Acid and N, N–(dihydroxymethyl) urea Derivatives on the
Properties of Rigid Polyurethane-Polyisocyanurate Foams; WU UKW: Bydgoszcz, Poland, 2011. (In Polish)
49. Dick, C.; Dominges-Rosado, E.; Eling, B.; Liggat, J.J.; Lindsay, C.I.; Martin, S.C.; Mohammed, M.H.; Seeley, G.;
Snape, C.E. The flammability the flammability of urethane-modified polyisocyanurates and its relationship
to thermal degradation chemistry. Polymer 2001, 42, 913–923. [CrossRef]
50. Janik, H. Progress in the studies of the supermolecular structure of segmented polyurethanes. Polimery 2010,
55, 421–430. [CrossRef]
Appl. Sci. 2019, 9, 2663 23 of 23

51. Thirumal, M.; Khastgir, D.; Singha, N.K.; Manjunath, B.S.; Naik, Y.P. Water blown rigid polyurethane foam. J.
Appl. Polym. Sci. 2008, 8, 1810–1817. [CrossRef]
52. Piszczyk, Ł.; Hejna, A.; Formela, K.; Danowska, M.; Strankowski, M. Morphology, mechanical and thermal
properties of flexible polyurethane foams modified. Polimery 2014, 59, 783–791. [CrossRef]

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