Construction and Building Materials 185 (2018) 285–292

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Construction and Building Materials

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

Lightweight hybrid organic-inorganic geopolymers obtained using

polyurethane waste
L. Bergamonti, R. Taurino, L. Cattani, D. Ferretti, F. Bondioli ⇑
Department of Engineering and Architecture, University of Parma, Parco Area delle Scienze 181/a, 43124 Parma, Italy

h i g h l i g h t s g r a p h i c a l a b s t r a c t

Recycling of polyurethane wastes is

proposed.

New lightweight hybrid organic-
geopolymers are developed.

Metakaolin-based geopolymers are
obtained by adding polyurethane
foam wastes.

The hybrid geopolymer composites
show good mechanical and thermal
properties.

Lightweight hybrid geopolymer
composites can conveniently
proposed as insulation building
materials.

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

Article history: Lightweight geopolymers from wastes with reduced thermal conductivity have become an important
Received 26 January 2018 trend for green buildings sector. In this work, organic-inorganic hybrid geopolymers were prepared from
Received in revised form 15 May 2018 polyurethane powders wastes (polyurethane foam and polyisocianurate foam). Chemical, physical and
Accepted 2 July 2018
mechanical properties of geopolymers, manufactured with different percentages of polyurethane wastes
are reported and discussed. The FTIR spectroscopy allowed to verify the influence of both polyurethane
powders on the framework structure revealing H-bonds between polyurethane and inorganic phase.
Keywords:
Flexural and compressive strengths showed that content and typology of the used polyurethane wastes
Hybrid geopolymers
Polyurethane foam wastes
affected the material behavior. The strength of hybrid geopolymers was maximized with polyisocianu-
Mechanical properties rate foam waste addition in a concentration lower than 14% in weight. Thermal conductivity was carried
Thermal conductivity out on appropriate samples, showing that the hybrid geopolymers exhibit satisfactory isolation proper-
Lightweight geopolymers ties. The new materials proposed in this work represents an innovative solution, enhancing the thermal
resistance of the buildings by using a waste intended for landfill.
Ó 2018 Elsevier Ltd. All rights reserved.

1. Introduction and polyisocyanates [1]. They can be considered as copolymers

Polyurethanes (PUs) represent an important class of both ther-
moplastic and thermoset polymers, characterized by the urethane
group as a common feature. Their mechanical, thermal and chem-
ical properties can be tailored by the reaction of various polyols
⇑ Corresponding author.
E-mail address: federica.bondioli@unipr.it (F. Bondioli).
constituted by alternating hard and soft segments. Diisocyanate
and chain extender are the hard segments while the polyether or
polyester polyol flexible chain the soft segments [2].
Polyurethanes are known for their versatility with a wide range
of applications in different industries: building, automotive, sports,
naval and furniture [3]. In particular, rigid polyurethane foams are
the most industrially used insulators thanks to their low thermal
conductivity, high strength-to-weight ratio and low cost [4].

https://doi.org/10.1016/j.conbuildmat.2018.07.006
0950-0618/Ó 2018 Elsevier Ltd. All rights reserved.
286 L. Bergamonti et al. / Construction and Building Materials 185 (2018) 285–292
PUs, mainly in foams form, represent about the 7.5%
(15 Mt/year) of the total plastics used worldwide [5]. Due to the
environmental growing concern to landfill waste accumulation
and to the tight legislation on treatment and disposal, PU wastes
from district heating, end-of-life vehicles and many other sources
are receiving great attention for the development of new technolo-
gies to recycling this material [6–7].
During the process of rigid polyurethane foam products, 15% of
wastes is generally generated, the technology disposal of which
can be landfill, incineration, and recycling [8]. Landfill and inciner-
ation are not recommended except when it cannot use recycling
method [1,9]. The polyurethane waste recycling methods, compre-
hend energy recovery, chemical recycling and mechanical recy-
cling [10–12]. A common recycling method for PUs foam wastes
is the re-bonding process: foam wastes are milled into fine flakes,
blended with a powerful binder and then formed into boards or
moldings under heat and pressure [1,8]. The resulting products
are generally used for insulation boards in sound proofing applica-
tions. The problem of this solution is the low mechanical and phys-
ical performances of the obtained sample. Several studies reported
the application of PU wastes as fillers in the construction industry
[13–14]. PU foam powder can be directly added to concrete to
improve adiabatic effects, or to realize roof heat insulating layer
[8]. PU foam powder has been used for the production of light-
weight aggregate concrete composites [15–16]. Ben Fraj et al.
[17] reported the reduction of concrete density and the increasing
of porosity by addition of rigid polyurethane (PU) foam waste as
coarse aggregates (8–20 mm).
To the author’s knowledge no scientific study to date focuses on
using PU waste to manufacture lightweight geopolymer bricks.
However, knowing their potential as alternative binders, several
attempts have been made on the use of geopolymers to produce
mortars and concrete [18–20]. Geopolymers have received increas-
ing interest worldwide as an alternative to ordinary Portland
cement concrete due to cost increases in energy supply, require-
ments to reduce CO2 emission, limited reserve of limestones and
limited manufacturing growth of cement [21]. The additional moti-
vation for exploring this alternative is attributed to its high early
compressive strength, low drying shrinkage, superior durability
in aggressive environment compared to Portland cement concrete,
etc. [22]. Moreover, from the environmental point of view, devel-
opment and production of geopolymer materials from wastes has
been attracted growing importance in the last years [23]. The use
of granulated blast-furnace slag and fly ash in geopolymers has
been reported by many authors showing excellent mechanical
and physical properties [24]. Bayer liquor and fly ash have been
utilised by E.J. Jamieson and coworker [25] to obtain a new class
of ambient-cured construction geopolymers with compressive
strength higher than 30 MPa associated to a very low carbon foot-
print. An increase of ductility property of geopolymers has been
obtained by T.A. Kua et al. [26] by adding various mix designs of
spent coffee grounds, fly ash and slag.
However, there are a few papers on the production of waste-
based lightweight geopolymers [27–28]. In this direction, some
studies have proposed lightweight geopolymers using rice husk
ash and diatomaceous earth aggregates [29] or recycling light-
weight block wastes mixed with lignite fly ash [30]. They obtained
mean bulk density of 880 kg/m3 and compressive strength of
1.5 MPa in the optimized condition. Arellano Aguilar et al. [31]
obtained aerated geopolymer concrete by mixing metakaolin and
fly ash. The density of concretes was reduced by aeration by adding
aluminium powder and in some cases by adding lightweight aggre-
gate derived from blast furnace slag. Densities were set at 600, 900,
and 1200 kg/m3 and maximum compressive strength of about 3.5,
8, and 16 MPa was reached with these densities, respectively.
In this scenario, this study is a preliminary investigation on the
possibility of utilizing PU powdered waste as raw materials in the
production of hybrid geopolymers. For this research, geopolymer
and PU powders were combined together to study the effect on
the geopolymers properties and the feasibility of using this waste
as fillers in geopolymers.
2. Experimental
2.1. Materials
Kaolin (Al2Si2O5(OH)4), sodium hydroxide (NaOH) and sodium trisilicate
(Na2O3SiO2) were purchased by Sigma Aldrich. Two different powders, CorafoamÒ
PIR50 (Polyisocyanurate foam) and CorafoamÒ CP125 (Polyurethane foam), were
provided by DUNA Corradini (Italy). The density of CorafoamÒ PIR50 and CorafoamÒ
CP125 were 0.110 and 0.085 g/cm3, respectively.
2.2. Samples preparation
Metakaolin was obtained by calcination of kaolin at 550 °C for 10 h based on the
work of Ilić et al. [32]. The alkaline solution was prepared by mixing sodium
hydroxide solution (6M) and sodium silicate solution (2.5 M) in a ratio of 4:1.
The preparation of geopolymers paste samples was obtained by mixing meta-
kaolin powder and alkaline activator solution with a mass ratio of 3:1 as suggested
by Wang et al. [33]. The hybrid geopolymers were obtained adding different per-
centages of polyurethane PU powders (0, 9, 12.5, 14, and 20 wt% with respect meta-
kaolin), to the metakaolin-based geopolymers matrix. Resulting slurries were
stirred mechanically for about 10 min at 750 rpm to reach good homogenization
and then were poured in rectangular and cylindrical silicon molds and vibrated
for 2 min to remove the entrapped air. The molds were left at room temperature
for 24 h and successively placed in an oven at 40 °C. Demolding was carried out
after 24 h and the samples were stored in a desiccator for 28 days. The so obtained
samples were then fully characterized.
Depending on the quantity and type of added PU (PIR50 or CP125), the samples
were coded GeoXy where, X is the kind of PU (P for PIR50 and C for CP125) and y is
the percentages of PU with respect to metakaolin.
2.3. Sample characterization
Samples chemical features were studied by FT-IR analysis, recorded on Nicolet
5700 FT-IR Spectrophotometer (Thermo Electron Corp). 32 scans between
4000 cm1 and 400 cm1 were averaged for each spectrum at intervals of 1 cm1.
FT-IR spectra were generated by pressing 500 mg of dried sample on KBr crystal.
XRD patterns were obtained by Bruker D2 PHASER X-ray diffractometer with
1-dimentional LYNXEYE detector, using Cu-Ka radiation at 40 kV and 10 mA, at
0.2°/s scan rate (in 2h) in the range 0–80°. RT measurements were obtained with
the powdered geopolymer samples spread on a conventional glass sample holder.
Powdered silicon reflections were used for 2h calibration. The identification of crys-
talline phases was made under comparison with data on the JCPDS files.
Morphological observations were performed on geopolymer cross-section by a
Scanning Electron Microscope (SEM) JEOL 6400 equipped with Energy Dispersive
X-Ray Microanalysis System (EDS) Oxford-INCA, with Si(Li) window-less detector.
Apparent density was measured by considering the weight and the dimension
of specimens. The results were the mean of three measurements. The experimental
errors in the apparent density evaluations was ±0.03 g/cm3.
Flexural strength was measured by means of three-point-bending tests using a
universal testing machine (MTS model DY3X/M with a 10 kN load cell). Tests
were performed controlling the displacement of the actuator with a speed of
0.05 mm/min. Young’s modulus was computed from the initial slope of the load –
flexural displacement curve. Flexural displacements were measured using Digital
Image Correlation (DIC), which permitted to observe and to remove possible rigid
body displacements of the specimens. Specimens had nominal dimensions
span  base  height equal to 50 mm  10 mm  5 mm.
Because of limitations of our laboratory production chain of geopolymers, spec-
imen had a maximum thickness of 6 mm. This small value required small flexural
specimens and did not permit to perform standard compression tests on cubes or
cylinders (e.g. according to EN-1015-11:2007 [34]). For this reason, Double Punch-
ing Test (DPT) as specified by DIN 18555-9:1998 [35–36] were performed using the
universal testing machine employed for bending tests, controlling the displace-
ment. Tests were performed on disks of diameter 50 mm and thickness 6 mm.
The steel punches had a diameter of 20 mm and the displacement speed was
0.45 mm/min. Punching strength rDPT was obtained by dividing the ultimate load
by the area of the punch.
The thermal conductivity was measured by adopting a parameter estimation
procedure [37] based on the solution of the inverse heat conduction problem within
the sample. A thin copper plate, connected to a power supply, was used as a plane
 L. Bergamonti et al. / Construction and Building Materials 185 (2018) 285–292 287

heat source which was applied to one side of the sample and thermal transient
response was measured on the opposite side of the specimen through multiple
thermocouples. The sample, sizing 20 cm  12.5 cm  0.9 cm, was thermally insu-
lated by adopting a rock wool layer with a thickness of 5 cm, in order to minimize
the heat exchange to the environment.
In Fig. 1 it is reported a sketch of the experimental set up.
As far as, the measured temperature variation is strongly dependent on the
thermal transport properties of the material in contact with the copper plate, by
monitoring this temperature change with time, it is possible to obtain useful data
on the thermal conductivity and thermal diffusivity of the studied material. In par-
ticular, the acquired temperature distribution was employed as input data of the
inverse heat conduction problem in the wall under the solution approach based
on least squares minimization [38].
In order to implement the estimation method, a 3-D numerical finite element
model of the whole test section (sample, metal plate, thermal insulation) was
implemented within the Comsol MultiphysicsÒ environment.
Calling Y (Yi = measured temperature at time i, i = 1. . .n) the temperature data
experimentally measured on the sample surface and T(k) the corresponding simu-
lated temperature obtained from the solution of the numerical problem by impos-
ing a value of thermal conductivity k, the parameter estimation problem is solved
by minimizing the following function [37]:

X
n
2 Fig. 2. Comparison between measured and restored temperature distribution
S¼ ðY i  T i ðkÞÞ ð1Þ
(GeoC20 sample).
i¼1

Therefore, the value of thermal conductivity k that permits to minimize the tar-
get function S represents the best approximation of the real value that characterize
the studied sample. In this paper, the minimization of S was performed by the
Nelder-Mead algorithm [39] that is a well-known algorithm for multidimensional
unconstrained optimization.
In Fig. 2 it is reported, for a representative case, the comparison between the
experimentally measured temperature and the restored temperature distribution,
during time t, obtained by adopting the thermal conductivity found with the above
presented procedure.

3. Results and discussion

3.1. Raw materials characterization

The FT-IR spectra of metakaolinite and polyurethanes used as

filler are reported in Fig. 3. In the FTIR spectrum of metakaolin,
no bands due to chemically bonded hydroxyl groups are present,
confirming that dehydroxylation of kaolin to metakaolin, in the
calcination process, occurs [40]. The broad and strong band at
1050 cm1 is assigned to the asymmetric stretching of Si-O-T
(T can be Si or Al), while the symmetric stretching vibration of
Si-O-T is found at 650 cm1 [41]. The six coordinated Al-O stretch-
ing vibration is located at 800 cm1 [42]. The absence of AlAOH
bands at 920 and 940 cm1 confirms the formation of metakaolin
[40].
The FTIR spectrum of powdered PIR50 PU foam exhibits at
2275 cm1 the peak due to the stretching vibration of the residual
isocyanate groups (N@C@O) band [43]. The NAH stretching
(hydrogen bonding N-H   O-C@O) and in plane bending vibrations
of urethane groups correspond to the broad absorption band
centered at about 3330 cm1 and to the strong peak at
1510 cm1 [44]. The strong absorption peaks at 1710 cm1 and
1208 cm1 are attributed to the stretching vibration of C@O
(urethane carbonyl hydrogen bonded in the polymer chains) and
Fig. 1. Sketch of the experimental set up.
Fig. 3. FTIR spectra of pure reagents.
C-O-C, respectively [45]. The weak peak at 3050 cm1, the medium
absorption peak at 1594 cm1 and the several weak peaks in the
range 767–916 cm1 are due to the @CH and C@C stretching vibra-
tion, and bending vibration of CAH of aromatic ring from the start-
ing isocyanate reagent, respectively [46]. The peaks between 2950
and 2850 cm1 are caused by the stretching vibration of aliphatic
C-H and CH2 in the main chain of PU. The sharp and strong peak
at 1405 cm-1 is to bending vibration of aliphatic C-H2. The spec-
trum of the CP125 PU foam is very similar to that of PIR50. The
main difference is found in the less the intensity of the vibrational
bands assigned to isocyanate group at 2275 cm1.
The results of the mineralogical analysis of metakaolin
(not reported here) revealed a broad band between 18° and 25°
2h attributed to the amorphous structure of metakaolin induced
by the calcination of the kaolin [33]. The main crystalline
phases of starting kaolin, i.e. quartz (SiO2) [01–085–0457], musco-
vite (KAl2(Si3Al)O10(OH)2) [00–007–0042], microcline KAlSi3O8
[00–019–0932] and albite (AlNaO8Si3) [01–083–1610], remain
almost intact [32]. The peaks at °2h=12.44 and 24.95, by the reflec-
tion planes [001] and [002] of kaolinite crystal [47], respectively,
completely disappear after thermal treatment. By XRD results
can be affirmed that the metakaolin is a mix of hypocrystalline
and amorphous structure [48].
288 L. Bergamonti et al. / Construction and Building Materials 185 (2018) 285–292
3.2. Geopolymer characterization
In the FTIR spectra of the geopolymers (Fig. 4), signals at
3450 cm1 and 1650 cm1, can be attributed to the stretching
and bending vibration of the OH groups due to the adsorbed water.
The Si-O stretching frequency is very sensitive to the substituents.
After geopolymerization, the strong band at 1050 cm1, in meta-
kaolin, due to the mas of SiAOAT bond, is shifted at lower
wavenumber (about 70 cm1). The medium band at 798 cm1
attributed to the four coordinated Al(IV)-O stretching vibration
decreases in the geopolymeric product. The new band at
850 cm1 is assigned to the bending vibration of SiAOH. In the
spectra of the composite geopolymers the characteristic vibration
bands of the polyurethanes are clearly detectable: NAH and C@O
stretching vibration from the urethane groups, and aromatic and
aliphatic CH stretching and bending vibrations from backbone
chain. It was worth noting the disappearance of the isocyanate
groups vibrations bands (at 2275 cm1 and 1450 cm1) may be
due to the reaction with reactive OH groups (SiOH, AlOH, H2O)
[2]. In the spectrum of the GEOP20 the bands due to the OH stretch-
ing and bending vibrations completely disappeared while in the
Fig. 4. FTIR spectra of geopolymer products.
Fig. 5. XRD spectra of geopolymers Geo0, GeoP20, GeoC20. q – quartz, m – muscovite, al – albite, hy – katoite, f – k-feldspar.
case of GEOC20 the bands decreased with respect to GEO0 but are
still detectable.
The XRD patterns of hybrid-geopolymers obtained with differ-
ent organic phase content, after stored in air for 28 days, are
reported in Fig. 5. According to the XRD results, there are no clear
differences between the X-ray diffractograms of the prepared
geopolymers. Several crystalline phases were observed in the syn-
thesized materials. In particular, the characteristic diffraction
peaks of quartz (SiO2) are retained after geopolymerization, which
suggests that quartz did not participate in the reaction of geopoly-
merization [48]; this is mainly due to the low dissolution rate of
crystalline quartz into alkaline media [49]. All samples contain
clays mineral, identified as muscovite and crystalline components
as microcline from the metakaolin. Moreover, hydrated products,
as sodium and calcium aluminum silicate hydrate were found in
the geopolymeric products. Due to the reorganization of Al-O and
Si-O network from metakaolinite following the reaction with the
alkaly activator solution, small percentage of sodium aluminum-
silicate are revealed [50]. Additionally, the samples have an amor-
phous halo between approx. 25–35° 2h which can be associated
with the unordered geopolymer structure [51].
Microstructures of geopolymer samples were observed by scan-
ning electron microscopy (SEM) (Figs. 6 and 7). The SEM analysis
was performed only on samples with 0 wt% and 20 wt% of PU pow-
ders. The Geo0 (Fig. 6a) exhibit a uniform and compact structure
that includes interconnected pores (50–60 lm) and some dis-
persed larger capillary pores, attributed to air bubbles that remain
entrapped into the pastes during the reactions of dissolution and
polycondensation [52]. The hybrid geopolymers are characterized
by high porosity that depend to the PU powders typology added
in the inorganic matrix. As showed in Fig. 6b, GeoC20 sample shows
many small pores regularly distributed in the matrix, while GeoP20
(Fig. 6c) shows a compact structure with pores with inhomoge-
neous size distribution. The PU powders, while being from a
microstructural point of view a heterogeneous and anisotropic
material, are homogeneously embedded in the inorganic matrix
and then responsible for the new organization of the pore network.
In fact, this situation can explain the shift of the significant pores
bands from 60 lm, for Geo0 to 200–300 lm in the presence of
PU powders. These pores are important for obtain the lightweight
structure as reported below. In the Fig. 7, the difference of
the microstructure between GeoP20 and GeoC20 samples can be
 L. Bergamonti et al. / Construction and Building Materials 185 (2018) 285–292 289

Fig. 6. SEM micrographs at 100 of: (a) Geo0, (b) GeoC20 and (c) GeoP20.

in flexural strength and Young’s modulus E for a concentration of

Fig. 7. SEM micrographs at 50 of GeoP20 and GeoC20.
appreciated. Moreover, the micrograph of Fig. 7 shows that the
sample prepared with CP 125 has irregular structure and higher
porosity. No microcracks were observed in all samples.
The effect of PU content on the apparent density and porosity of
geopolymers is shown in Table 1.
Compared to the value of the reference sample, the apparent
density increased with PIR50 addition, this is more noticeable in
sample GeoP9. This can be associated with higher geopolymeriza-
tion degree as showed by FTIR and SEM results. On the other hand,
the addition of CIP125 in a concentration higher than 14 wt% lead
to a decrease of geopolymers samples density. This trend can be
explained by the combination of high porosity and lower density
of CP125 particles.
The effect of PU addition on mechanical properties of geopoly-
mer samples was investigated and the results are shown in Table 1.
The flexural strength development seems to depend mainly on the
PU typology despite the different amount of PU particles. In
fact, for GeoCx the addition of PU powders resulted in a decrease
CP125 higher than 9 wt%. The opposite is the case for GeoPx sam-
ples where the addition of PIR50 led to improved flexural strength
and Young’s modulus. In particular, some of the developed compo-
sitions have rather high flexural strengths from 1.5 MPa for refer-
ence sample (Geo0) to 3.6 MPa for GeoP12.5 sample.
Punching strength rDPT is usually related to compressive
strength of thin layers of mortar used for masonry assemblage,
when cubic samples of suitable dimensions are not available [53].
Fig. 8 shows the average punching strength rDPT of samples
with 9 wt% and 20 wt% PU concentration. It can be seen that there
is a good improvement in the ultimate punching load capacity due
to the addition PU fillers. According to these results, the ultimate
punching strength of geopolymers composites with 20 wt% of PU
increased by about 55% in comparison with the control sample
(Geo0).
The thermal conductivity was evaluated for Geo0, GeoP20 and
GeoC20 samples (Table 2).
In both cases of GeoP20 and GeoC20 samples, the addition of
polyurethane powder permits to reduce the thermal conductivity
respect to the case of Geo0 specimen. In fact, the thermal conduc-
tivity of the hybrid geopolymers was reduced from 0.40 W/m
(Geo0 sample) to 0.30 W/m K (GeoC20) with a decrease of 10% for
GeoP20 sample and of 25% for GeoC20 respectively.

Table 1
Mechanical properties: apparent density (qa), flexural strength (rf), Young’s
Fig. 8. Punching strength of the samples with dosage of 0 wt%, 9 wt% and 20 wt% of
modulus (E).
PU wastes.
Sample qa (kg/m3) rf (MPa) E (GPa)
Geo0 970 1.5 ± 0.2 892 ± 60
GeoP9 1149 2.7 ± 0.5 1466 ± 452 Table 2
GeoP12.5 1020 3.6 ± 0.4 2749 ± 137 Thermal conductivity and total porosity (%) of geopolymers samples with 0 wt% and
GeoP14 1057 2.9 ± 0.3 1753 ± 320 20 wt% of PU wastes.
GeoP20 1030 2.6 ± 0.5 1048 ± 79
Samples Total porosity (%) Thermal conductivity (W/mK)
GeoC9 1126 4.0 ± 0.6 1604 ± 327
GeoC12.5 1011 1.4 ± 0.1 491 ± 42 Geo0 14.9 ± 0.7 0.40 ± 0.04
GeoC14 923 1.0 ± 0.2 575 ± 26 GeoP20 10.3 ± 0.3 0.36 ± 0.04
GeoC20 885 1.5 ± 0.1 852 ± 53 GeoC20 12.7 ± 0.5 0.30 ± 0.03
290 L. Bergamonti et al. / Construction and Building Materials 185 (2018) 285–292

3.3. Discussion issue. Thus, the adoption of innovative solutions for increasing
the thermal resistance of the buildings represents an interesting
FTIR spectra confirmed the formation of geopolymers products research item. With this aim, the decrease of thermal conductivity
with 3d network structure [54], after polycondensation reaction of geopolymers with PU powders waste represents an interesting
between SiO4 and AlO4. Infact, the changes in the original SiAO research result. In particular, the best thermal insulation properties
chemical environment due to the formation of SiAOAAl bonding, of hybrid geopolymers could be correlated to the lower apparent
resulted in different chemical shift and in a reduction or disappear- density and higher porosity respect to the reference sample. Infact,
ance of some characteristic bands in FTIR spectra. This confirms the the higher porosity of the microstructure, because of air trapped
growing of polysialate polymers and the formation of crosslinking into the pores, permits to obtain a better thermal insulating behav-
network overlay the polysilicate chains [42]. The higher reactivity ior. Another possible explanation it could be found, as observed by
of the PIR50 (polyisocyanurate foam) can be due to the relevant Pia et al. [58], that a greater amount of pores of smaller size pro-
amount of the N@C@O groups that are very reactive in presence duces a lower thermal conductivity. As it is possible to see from
of acidic hydrogen. The formation of interactions with organic Fig. 7 the structure of GeoC20, even if presents pores of lower
phases can be indicated from the lowering of the SiAO group dimension, it is characterized by more regularly and densely dis-
stretching frequency by 50–80 cm1 due to the hydrogen bond tributed porosity which can contribute to increase the insulation
with OH or NH groups. [48]. Moreover, the change in the shape [59].
of the AOH stretching band centered at 3440 cm1 and its shift
to lower wavenumbers for hybrids geopolymers suggested the for-
4. Conclusions
mation of new hydrogen bonds.
The nature of interactions between the organic and the inor-
Due to high stability in the environment of the polyurethane
ganic component allows to classify the obtained products as
foam wastes, their accumulation generates elevated landfill pollu-
first-class hybrids (materials with weak interphase bonding), in
tion. The recycling of polyurethane wastes would be limiting the
agreement with the classification of the organic-inorganic hybrid
congestion and pollution by PUs waste.
materials proposed by Judeinstein & Sanchez [55].
Lightweight hybrid organic-geopolymers were successfully
The different final chemical, physical and mechanical properties
obtained by using polyurethane industrial wastes. Two typologies
of hybrid geopolymers, obtained in this work, can be explained by
of PU foam powders were employed: polyisocyanurate foam PIR50,
the different reactivity of PU powder groups with metakaolin. In
highly reactive due to consistent amount of free isocyanate groups
particular, the higher reactivity of PIR50 can be assigned to the
(as revealed by FTIR spectroscopy), and polyuretane foam CP125
presence of isocyanate groups. For example, if GeoP20 and GeoC20
with lesser content of free isocyanate groups. Interaction between
samples are compared, a homogeneous amorphous structure and
PU powders were suggested by the relevant shift of the silicon IR
higher density values in GeoP20 can be observed, that means that
absorption band.
the geopolymerization process was successfully carried out. In
Flexural and compressive strengths showed that content and
addition, the decrease of geopolymers samples density with
typology of the used PU powders affected the material behavior.
CIP125 concentration higher than 14 wt% can be explained by
In particular, the strength of hybrid geopolymers was maximized
the combination of high porosity and lower density of CP125 par-
with the addition of PIR50 foam waste in a concentration lower
ticles. The higher reactivity of PIR50 allows also to obtain an
than 14% in weight. This suggested that the strengthening mecha-
increase of mechanical properties. However, when the amount of
nism is focused on the reactions at the interfacial zone between
PIR50 increased after certain limit (14 and 20 wt%), flexural
matrix and PU particles.
strength tended to decline, although was higher than the control
Thermal conductivity determined on samples with 20 wt% of PU
sample (Geo0). This behavior is due to a porosity increase that
waste showed an improvement with respect to Geo0 reference
affects the cohesion and hence reduces the flexural material resis-
specimen, exhibiting satisfactory isolation properties.
tance. It can be seen that mixtures having CP125 higher than 9%
The hybrid geopolymer composite obtained by adding PU foam
achieved slightly less flexural strength than the control geopoly-
wastes, proposed in this work, represents an innovative solution,
mer, because effected by higher porosity.
which enhances the thermal resistance of the buildings, and also
The increase of geopolymer reaction degree in the presence of
contributes to lower insulation costs. Moreover, due to the envi-
PU powders was confirmed by punching strength results. In partic-
ronmental and energy concerns, the reuse of polyurethane foams
ular, the substitution of metakaolin with PIR50, favoring the
from industrial wastes offers a sustainable waste recycling process,
geopolymerization reaction, produces final geopolymeric products
alternative to landfill or incineration.
with the best punching strength resistance. This constitutes an
interesting organic-inorganic hybrid composite, showing interest-
ing mechanical properties and a considerable reduced brittleness Conflict of interest
with respect to the geopolymeric matrix. The PU phase adsorbs
an aliquot of the load by plastic deformation and performs a tough- None.
ening effect by a typical crack deviation mechanism delaying the
growth of the microcracks [56]. It must be recalled that mechanical
Acknowledgements
properties were measured on small specimens whose size did not
obey to standard prescriptions. For this reason, a size effect on
The authors would like to thank DUNA-Corradini S.P.A. for sup-
results is plausible and comparisons with mechanical properties
plying the polyurethane materials used in this work and Dr.
measured in other works on specimens with different size are
Alfredo Notartomaso for experimental work during his master
not straightforward [57].
degree thesis.
Finally, in addition to mechanical and physical properties, it
was evaluated if the introduction of PU wastes in the studied sam-
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