Construction and Building Materials 229 (2019) 116930

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Construction and Building Materials

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

Pyrolysed cork-geopolymer composites: A novel and sustainable EMI

shielding building material
Rui M. Novais a,⇑, Manfredi Saeli a, Ana P.F. Caetano a, Maria P. Seabra a, João A. Labrincha a,
Kuzhichalil P. Surendran b, Robert C. Pullar a,⇑
a
Department of Materials and Ceramic Engineering/CICECO-Aveiro Institute of Materials, University of Aveiro, Campus Universitário de Santiago, 3810-193 Aveiro, Portugal
b
Materials Science and Technology Division, CSIR-NIIST, Industrial Estate, Trivandrum 695019, India

h i g h l i g h t s

 Recycled cork wine stoppers were used as a highly sustainable carbon source.
 An industrial waste was used as main raw material in the geopolymers production.
 First ever report on cork-geopolymer composites for EMI shielding applications.
 Maximum total shielding effectiveness values ranging from 13.8 to 15.9 dB.
 This highly sustainable material may ensure large-scale electromagnetic protection.

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

Article history: In this investigation, and for the first time, pyrolysed sustainable cork was used to produce waste-based
Received 4 February 2019 geopolymer-cork composites with enhanced electromagnetic interference (EMI) shielding properties. The
Received in revised form 22 August 2019 influence of the pyrolysed cork amount and the geopolymer porosity on the EMI shielding ability of the
Accepted 9 September 2019
composites was studied. The maximum total shielding effectiveness (SET) values achieved by these novel
building materials ( 13.8 to 15.9 dB) are equal to any other reported geopolymer microwave (MW)
absorbers over the X-band, despite containing much lower carbon content. In addition, our composites
Keywords:
were produced using an industrial waste (biomass fly ash) as raw material and recycled wine stoppers
Inorganic polymer
Construction
as a carbon source (2.5–3.75 wt%). This strategy is different from those implemented in the only other
Microwave absorption reported MW absorbing geopolymers, which used standard commercial chemical precursors, and the
Cork added carbon component is also a non-renewable commercial product, added in much greater quantities
Composite (10 more). Therefore, our approach not only decreases the consumption of virgin raw materials (e.g.
kaolin), but also enhances the global sustainability of the construction sector.
Ó 2019 Elsevier Ltd. All rights reserved.

1. Introduction exposure to such radiation, but also to ensure the protection of

The exponential increase in the use of electronic devices
observed over the past years, associated with the era of the Inter-
net of things (IoT) [1], has raised concerns regarding the unprece-
dented levels of electromagnetic radiation pollution [2] which may
affect human health [3,4], besides increasing the risk of electro-
magnetic interference (EMI) [5,6] in sensitive areas such as aero-
space and the aviation industry, the military and transport. It is
imperative to develop materials with the ability to shield/absorb
electromagnetic waves, not only to alleviate potential human
⇑ Corresponding authors.
E-mail addresses: ruimnovais@ua.pt (R.M. Novais), rpullar@ua.pt (R.C. Pullar).
electronic devices. Of particular interest are the microwave (MW)
frequencies, with wavelengths in the cm range (300 MHz–
30 GHz), including the X-band (8–12 GHz) used for military radar
and communications, some commercial and civil wireless and
satellite communications, motion sensors and speed detection
devices. 5G wireless devices will also operate at frequencies above
5 GHz.
Most research into microwave absorbing materials is aimed at
lightweight materials for coatings and applied panels, usually
based on foams or polymers containing some form of carbon
[7,8], conductive metals or magnetic absorbers such as ferrites
[9]. Amorphous and graphitic carbon is a well-known GHz/MW
absorbing material [10] and has been used as a powder (carbon
black, charcoal, graphite) [11,12], carbon fibres [13], carbon

https://doi.org/10.1016/j.conbuildmat.2019.116930
0950-0618/Ó 2019 Elsevier Ltd. All rights reserved.
2 R.M. Novais et al. / Construction and Building Materials 229 (2019) 116930
nanotubes (CNTs) [14,15], carbon nanorods [16] and graphene
[17]. However, the development of building materials with
enhanced EMI shielding properties would also be an excellent
strategy to restrict the electromagnetic radiation levels inside
buildings, and to ensure large-scale electromagnetic protection.
Clearly, in such materials low weight is less of an issue, secondary
to mechanical properties and chemical stability. Highly electrically
conductive carbon fibres and filaments [18–20], carbon nanotubes
(CNTs) [21,22] and graphene-coated CNTs [23] have been added for
EMI shielding to electrically insulating building materials such as
cement, other additives include metal fibres [24] and metal-
coated carbon fibres [25]. CNTs have also been added to concrete
[26,27]. Generally, a reasonable/practical microwave absorbing
material should have a shielding effectiveness (SE) of at least
10 dB, while an excellent shielding material should have a SE of
at least 30 dB (i.e. shielding efficiency 99.9%), and in cements
containing 0.5–1.5 vol% carbon filaments SE values of 29 to
37 dB have been achieved [18,20]. The feasibility of using Port-
land cement composites (the cement matrix itself presents poor
SE) for EMI shielding applications has been specifically considered,
using pyrolysed peanut and hazelnut shells [28], carbon fibres and
filaments [18,20,23], Fe3O4-carbon fibres [29], carbon nanotubes
[22], nano-Fe3O4 [30] and other additives [24,31,32].
Ordinary Portland cement is a highly used binder, being a com-
mon ingredient of concrete and mortars, and as such it is one of the
most widely used materials in construction. It is made mostly from
limestone. However, its production is responsible for a great
amount of greenhouse gases (5–7% of the total anthropogenic car-
bon dioxide emissions) [33], which has led to the pursuit of alter-
native and lower carbon footprint materials. One promising
alternative is the use of geopolymers [34–37] (also known as inor-
ganic polymers) [38–40], alkali activated aluminosilicate binders,
which may have a much lower carbon footprint [41] when the
raw materials and activator nature and content is carefully
considered.
However, the possibility of using geopolymer-carbon compos-
ites for electromagnetic radiation shielding, and in particular for
microwave shielding, has been rather neglected. In fact, there is
virtually no literature on this, the only example of a study on
alumino-silicate geopolymers being the work of Zhang et al. [42],
who added graphite to a metakaolin-based geopolymer prepared
using a potassium silicate solution as alkaline activator, and evalu-
ated the microwave absorption properties of the composites. They
looked at samples between 1.25 and 4.97 mm thick, with a massive
graphite content of up to 50 wt%, and over the frequency range of
2–18 GHz. A peak attenuation of 64.8 dB at 5.1 GHz was observed
when adding 40 wt% of graphite with a thickness of 4.15 mm.
However, in general high amounts of graphite were required to
achieve reasonable SE values, with narrow effective ranges of only
a few GHz, and none were very effective over the key X-band
region of 8–12 GHz. Although this demonstrated the feasibility of
using geopolymer composites for EMI shielding applications, the
very high graphite contents used (up to 50 wt%) were dictating
the microwave attenuation and the geopolymeric specimens were
cured at 70 °C for 7 days.
In this study, pyrolysed cork, coming from recycled wine
stoppers, was added in much lower amounts (up to 3.75 wt%), to
a waste-based geopolymer. The pyrolysed cork was directly added
to the geopolymeric slurry without the need for complex and
expensive procedures (e.g. ball-milling and ultrasonic stirring)
such as those used in [42]. The cork-composites were also synthe-
sised and cured at room temperature (20 ± 1 °C) using an industrial
waste (biomass fly ash), instead of commercial metakaolin, as the
main aluminosilicate source (70 vs 30 wt%), this being aligned with
the circular economy concept and contributing towards the
sustainment development.
Cork is a fully sustainable and 100% renewable precursor har-
vested without damaging the tree [43,44]. This is a crucial advan-
tage over other carbonaceous materials [45] and, therefore, its
incorporation after pyrolysis into building materials for EMI shield-
ing applications, instead of other environmentally unsustainable
precursors (e.g. carbon nanotubes, graphene, carbon fibre), is an
environmentally friendlier strategy. In fact, cork pyrolysis can be
considered a null carbon footprint process, since the CO2 emitted
during pyrolysis will be neutralised by that absorbed by the tree
to regenerate the cork bark. Moreover, in this study recycled cork
wine stoppers, instead of natural/unprocessed and high quality
cork (known as reproduction cork [46]), were used to produce
the pyrolysed cork, which further decreases the process production
cost and increases its global sustainability. Recycled cork wine
stoppers may be a highly abundant and low cost precursor for
EMI shielding applications. In fact, worldwide stoppers production
reaches a striking 12 billion units/year, which may be recycled and
reused in other applications [47]. Over 12 billion cork stoppers are
produced each year. Yet, despite being recyclable, cork wine stop-
pers cannot be reused by the wine industry due to their lower
quality and contamination after use, and the small proportion
which are recycled are used (after processing) in the production
of other products such as badminton and tennis rackets, and
cricket balls, amongst others. In addition, recycled cork wine stop-
pers can be bought by the cork industry, and then after being
ground and heat treated, can be used to produce cork agglomerates
for insulation applications. Nevertheless, their use as a carbon
source in the production of eco-friendly EMI shielding materials,
as proposed here, will attribute value to this material. In addition,
and despite recent efforts promoting the collection and recycling of
cork wine stoppers (e.g., ‘‘Greencork” in Portugal, ‘‘ReCORK” in USA
and ‘‘Cork Recycling Program” in Australia) [48], this process is still
in its early days. In fact, over the past 11 years the ‘‘ReCork” pro-
gram has collected and recycled roughly 105 million corks, corre-
sponding to around 10 million/year and to 0.08% of the
worldwide stoppers production per year. This shows that the
majority of used wine corks is still not recycled, and therefore can-
not be used by the industry. This means that most of the used corks
are still lost in landfills. For that reason, innovative management
strategies that might encourage the recycling of used cork stoppers
are eagerly pursued.
Besides the remarkable sustainability of cork and it’s very low
apparent density, both crucial features in EMI shielding materials,
cork also has a unique microstructure consisting of hollow polyhe-
dral cells, with a hexagonal honeycomb shape (15–20 lm diam-
eter) when viewed from the radial direction coming out of the tree,
and a rectangular shape (45 lm length, resembling a brick wall)
when viewed from the transverse side or top directions. The
hexagonal honeycombs are expected to aid the internal reflection
and absorption of the microwaves within the structure. Further,
for very high shielding performances, honeycomb panel wafers
are commonly used which are usually costly and heavy. Only in
such structures can important design considerations like ventila-
tive cooling and shielding be combined. Our attempt is to explore
a similar air permeable shielding structure using naturally occur-
ring honeycomb materials.
This investigation intends to act as a proof-of-concept, demon-
strating the possibility of using green, low cost, and environmental
friendly cork-geopolymer composites as an innovative EMI shield-
ing building material. The influence of the cork amount and the
geopolymer porosity on the EMI shielding ability of the composites
was studied. The results reported here are expected to be extended
to other cork sources besides wine stoppers. One exciting possibil-
ity could be the use cork powder wastes produced in substantial
amounts by the cork industry, which have low economic value
and are mainly used to produce energy by their combustion [46].
 R.M. Novais et al. / Construction and Building Materials 229 (2019) 116930
2. Experimental conditions
2.1. Materials
Recycled cork wine stoppers were used in this study. The cork
samples were pyrolysed under nitrogen in a graphite furnace, fol-
lowing previous works by the authors [44,49]. The samples were
heated at 10 °C/min up to 900 °C, kept for 30 min at this tempera-
ture and then cooled down to room temperature, all while under a
flow of N2. The pyrolysed cork was then ground in a mortar and
sieved below 75 mm.
Biomass fly ash waste was used as the main source (70 wt%) of
reactive silica and alumina, while metakaolin (ArgicalTM M1200S;
Univar) was used in lower amounts (30 wt%) as an additional alu-
minosilicate source in order to achieve suitable SiO2/Al2O3 molar
ratios. The fly ash waste, supplied by a Portuguese paper and pulp
company, was used as-received, despite the coarse particle size
(containing particles of a few mm) which is detrimental to the
geopolymer’s compressive strength. The potential of these ashes
as an aluminosilicate source for geopolymer production, has been
demonstrated by the authors previously [50–52].
The direct use of the ashes in the geopolymer synthesis, without
performing any expensive sieving or milling step, decreases the
geopolymer production cost, and may allow an easier industrial
scale-up application.
The chemical activation of the aluminosilicate sources was per-
formed using a mixture of sodium silicate (SiO2/Na2O = 3.2; Qui-
mialmel) and 10 M sodium hydroxide (ACS reagent, 97%,
Honeywell) in 3:1 wt% proportion. The SiO2/Na2O ratio of the acti-
vating solutions was 1.7. This ratio was selected considering pre-
liminary tests in which the influence of the sodium silicate to
sodium hydroxide in the geopolymers’ compressive strength was
evaluated.
A hydrogen peroxide solution (Alifar, 30 vol%, Laboratório
Aliand) was used as a foaming agent. This foaming agent was used
for the first time to induce porosity in geopolymers by Bell and Kri-
ven [53].
2.2. Cork-geopolymer composite synthesis
In this study, and following previous work by the authors [54], a
reference composition without added pyrolysed cork was synthe-
sised (see details in Table 1). Then, six other compositions were
prepared containing various amounts of cork and foaming agent,
to evaluate the influence of the pyrolysed cork and foaming agent
amount on the EMI shielding behaviour of the composites.
The cork-geopolymer composites synthesis involved two steps:
in the first, the geopolymeric slurry was prepared, while in the sec-
ond, the pyrolysed cork and the foaming agent (amount depending
on the composition) were added to the slurry. Manufacture
involved five steps: the 1st step was performed manually, while
the others were carried out using an intensive mixer (KichenAidÒ),
Table 1
Mixture composition of the cork-inorganic polymer composites.
Sample ID Description
Matrix Geopolymer
C2.5 Composite with 2.5% cork
C3.75 Composite with 3.75% cork
LC2.5_1 Lightweight composite with 2.5% cork and 1% H2O2
LC3.75_1 Lightweight composite with 3.75% cork and 1% H2O2
LC2.5_2 Lightweight composite with 2.5% cork and 2% H2O2
LC3.75_2 Lightweight composite with 3.75% cork and 2% H2O2
3
having a geometry in accordance with DIN 1164, coupled with a
flat paddle.
a) hand mixing of biomass fly ash and metakaolin for 1 min
inside a plastic bag to ensure a uniform blend;
b) homogenisation of sodium hydroxide and silicate at 60 rpm
for 5 min;
c) mixture of the alkaline solution with the solid precursors at
95 rpm for 9 min;
d) adding the foaming solution (amount depending on the
composition, ranging from 1 to 2 wt%) and the cork to the
slurry and mixing at 135 rpm for 1 min to ensure homogene-
ity and bubbling;
e) pouring the slurry into the standard metallic moulds
(160 mm  40 mm  40 mm) and sealing with a plastic film.
The hardened specimens were unsealed, demoulded after 24 h,
and cured for 28 days until their characterisation. The manufactur-
ing process was all performed at ambient conditions (20 °C, 65%
RH) using a simple, reproducible and low-cost technique.
2.3. Materials characterisation
The microstructures of recycled cork wine stoppers, pyrolysed
cork and the geopolymer composites were evaluated by scanning
electron microscopy (SEM – Hitachi SU 70) equipped with energy
dispersion spectroscopy (Bruker EDS). Samples were coated in
gold/palladium. Optical analysis (Leica EZ4HD microscope) was
also performed on the cork-geopolymer composites to study their
morphology and pore size distribution.
The mechanical performance of the cork-geopolymer compos-
ites was determined at 28 days of curing, according to the Euro-
pean Standard EN 1015-11:1999 by means of compressive
strength tests. A universal testing machine (Shimadzu, AG-A), pro-
vided with a 20 kN load cell, running at a displacement rate of
0.5 mm/min, was used. Three replications were used to calculate
the mean values.
The apparent density was calculated by measuring the samples’
weight and volume. Three specimens were used, and the arith-
metic mean value was presented.
For the microwave shielding measurements in the X-band (8.2–
12.4 GHz), the studies were carried out on a vector network anal-
yser (Agilent E5071C) using the waveguide method. Total shielding
effectiveness (SET = SER + SEA) was calculated from reflection (SER)
and absorption (SEA) shielding effectiveness. Solid geopolymer
samples were machined into 10.1  22.9 mm rectangles, with 3,
5 and 7 mm thickness, using a Struers polishing machine (Struers
Tegramin 25), in order to make the sample suitably fit into the
waveguide slot coupled to the vector network analyser. SSE (speci-
fic shielding effectiveness) was calculated from density.
Elemental analysis for carbon, hydrogen and nitrogen was car-
ried out with a Tuspec Micro CHNS 630-200-200 elemental
analyzer.
Mixture proportion (wt%) Additives
Metakaolin Biomass fly ash Alkaline activator Cork (wt%) H2O2 (wt%)
15 35 50 – –
2.5 –
3.75 –
2.5 1
3.75 1
2.5 2
3.75 2
4 R.M. Novais et al. / Construction and Building Materials 229 (2019) 116930
3. Results and discussion
3.1. Cork and pyrolysed cork characterisation
Fig. 1 presents a digital photograph of the cork stopper before
and after pyrolysis. The pyrolysis induced some volume changes,
but the cork’s weight loss (70 wt%) is the most relevant feature
promoted by the thermal treatment under N2. The SEM micro-
graphs reveal the characteristic microstructure of cork, consisting
of hexagonal cells (radial direction, 20 mm diameter), which are
preserved in the pyrolysed cork. These features are in line with
previous reports on the pyrolysis of cork [49,55].
Not surprisingly, the EDS maps show that carbon and oxygen
are the most abundant elements – nevertheless, trace amounts of
sodium, potassium and chlorine were also detected. However, con-
sidering the poor sensitivity of the EDS technique for light ele-
ments such as carbon and oxygen, these maps should only be
considered as a rough estimate.
After pyrolysis, the cork was sieved below 75 mm, the apparent
density of this powder being 140 kg/m3. The result of the elemental
analysis shows that the pyrolysed cork is composed of carbon
(90.74 wt%), hydrogen (0.77 wt%) and nitrogen (1.67 wt%). The
EDS map shown in Fig. 1 and the EDS spectrum (not shown here)
show very similar oxygen and potassium content in comparison
with those seen in the cork precursor, 24% and 0.5%,
respectively.
3.2. Cork-geopolymer composites characterisation
A digital photograph of the reference geopolymer (matrix) and
two composites containing different amounts of pyrolysed cork
powder is shown in Fig. 2. As observed, the colour of the specimens
changes from light (left side specimen) to dark grey (right side
specimen) due to the incorporation of pyrolysed cork.
To evaluate the pyrolysed cork distribution within the matrix,
EDS elemental mapping was performed on the specimens, and rep-
resentative maps for dense and lightweight composites are shown
in Fig. 3. As observed, carbon is homogeneously distributed in all
the composites, which is beneficial for their EMI shielding ability.
Silicon and aluminium, the backbone elements of the geopolymeric
network, are also homogeneously distributed in the samples.
Fig. 4 presents optical micrographs of the pure geopolymer and
the various cork-containing composites. The micrographs of the
dense composites (prepared without foaming agent) show
the presence of some air voids introduced during mixing. Indeed,
the incorporation of pyrolysed cork powder into the geopolymeric
Fig. 1. Digital photograph, SEM micrographs and EDS elemental mapping of cork before and after pyrolysis.
Fig. 2. Digital photograph of the geopolymeric matrix and two dense cork-
geopolymer composites (C2.5 and C3.75).
matrix increased the slurry viscosity, hindering the release of air
bubbles after mixing. It should be highlighted that the specimens
were not vibrated after mixing, in an attempt to simplify the com-
posite synthesis.
When the foaming agent was added to the composites, a sub-
stantial increase in the number and volume of pores was observed,
due to the oxygen release coming from the foaming agent decom-
position in the alkaline medium. Interestingly, the amount of cork
powder affected the pore size distribution of the composites pro-
duced, with a coarser pore size distribution being observed for
higher foaming agent content (2 wt%) in the composites containing
less added cork (2.5 wt%). This was associated with the higher vis-
cosity of the slurry observed for the composite containing 3.75 wt%
cork, in comparison with its lower-cork-containing counterpart,
which prevented pore growth and coalescence. Despite this, the
apparent densities of both composites (coded as LC2.5_2 and
LC3.75_2) were similar as demonstrated in Fig. 5. The apparent
density of the cork-geopolymer composites is extremely relevant
when considering their use as building material. The lowest value
here reported (750 kg/m3) might be further reduced by increas-
ing the amount of foaming agent [56,57], decreasing the molarity
of the activator [58], and by decreasing the solid-to-liquid ratio
of the mixture composition [59,60]. This will be considered in
future work. Nevertheless, this density value is lower than that
in other reports on geopolymer foams [61] and mortars [62].
Fig. 5 presents the compressive strength and the apparent den-
sity of the various composites and of the reference composition. In
the dense composites, the incorporation of 2.5 wt% of pyrolysed
cork decreased the compressive strength by roughly 31%, from
 R.M. Novais et al. / Construction and Building Materials 229 (2019) 116930
Fig. 3. EDS elemental mapping of dense (a and b) and lightweight (c) cork-geopolymer composites containing a) 2.5 wt% (C2.5) and (b and c) 3.75 wt% cork (C3.75 and
LC3.75_2, respectively).
Fig. 4. Optical microscopy micrographs of the matrix and the various dense and
lightweight cork-geopolymer composites.
22.2 MPa (geopolymer matrix) to 15.3 MPa. This was expected, and
is attributed to the significantly lower density and strength of this
additive in comparison with the geopolymeric matrix. In line with
this remark, the apparent density of this composite (C2.5) was 8%
lower than that of the matrix. A further increase in the cork content
(to 3.75 wt%) did not significantly modify the strength or density.
As expected, the lightweight composites showed much lower
strength than the matrix, a fourfold (to 5 MPa) and a six fold
(to 3.5 MPa) decrease being observed when adding 1 and 2 wt%
foaming agent to the composites, respectively, regardless of the
amount of pyrolysed cork. A similar trend was also observed for
apparent density, as shown in Fig. 5.
A SEM micrograph and the corresponding EDS spectrum of the
fracture surface of the 3.75 wt% cork-containing composite are
5
Fig. 5. Compressive strength and apparent density of the matrix and the various
cork-geopolymer composites (measured at the 28th day). Note: for clarity the dense
composites are highlighted in light-red, while the lightweight ones are in light-
green. (For interpretation of the references to colour in this figure legend, the reader
is referred to the web version of this article.)
presented in Fig. 6. The micrograph reveals an excellent interface
between the pyrolysed cork and the matrix. Moreover, it also
demonstrates that the pyrolysed cork preserved its microstructure
despite the high alkalinity of the geopolymeric matrix, showing
that the composites are durable and stable.
3.3. Microwave shielding capabilities
The total shielding effectiveness (SET) of the 3 mm thick sam-
ples is shown in Fig. 7a, and the range of values of SER, SEA and
SET for each 3 mm thick sample over 8.2–12.4 GHz are given in
Table 2. The first thing to note is that for all samples, SEA remained
more-or-less constant across the frequency range, while SER
showed a steep decline with increasing frequency and in all cases
converged towards similar values of around 2 dB above 12 GHz,
6 R.M. Novais et al. / Construction and Building Materials 229 (2019) 116930

Fig. 6. SEM micrograph and EDS spectrum of the fracture surface of the cork-geopolymer composite containing 3.75 wt% cork (C3.75) after the compressive strength test.

a) b) GP Matrix
GP Matrix 1% FA 2% FA C2.5 C3.75 5 mm thickness
C2.5 C3.75 12 LC2.5_1 LC3.75_1
10 LC2.5_1 LC3.75_1 LC2.5_2 LC3.75_2

Total Shielding Effectiveness SET (-dB)

Total Shielding Effectiveness SET (-dB)

LC2.5_2 LC3.75_2 11

9 10
3 mm thickness

8 9

8
7
7

6
6

5 5

4
4 8 9 10 11 12
8 9 10 11 12 Frequency (GHz)
Frequency (GHz)

c) GP Matrix d)
C2.5 C3.75
7 mm thickness
LC2.5_1 LC3.75_1 17
Total Shielding Effectiveness SET (-dB)

16 LC2.5_2 LC3.75_2 16
15
15 14
13
14 12
11
13 10
SET (-dB)

9
12 8
7
11
6
10 5
4
9 3
2
8 1
0
7
LC2.5_1 3mm
LC2.5_1 5mm
LC2.5_1 7mm
LC2.5_2 3mm
LC2.5_2 5mm
LC2.5_2 7mm
LC3.75_1 3mm
LC3.75_1 5mm
LC3.75_1 7mm
LC3.75_2 3mm
LC3.75_2 5mm
LC3.75_2 7mm
GP 3mm

GP 7mm

C3.75 3mm
C2.5 3mm
C2.5 5mm
C2.5 7mm

C3.75 5mm
C3.75 7mm
GP 5mm

8 9 10 11 12
Frequency (GHz)

Fig. 7. Total shielding effectiveness (SET) over the X-band of the matrix and the various cork-geopolymer composites for thicknesses of a) 3 mm, b) 5 mm and c) 7 mm. The
maximum SET value of every composite sample is compared in d). FA = addition of foaming agent only to geopolymeric (GP) matrix.

whatever the sample was made from. It was this trend in decrease and those with more cork added (3.75 wt%) had higher SEA, and
of SER which contributed most to the decrease in SET observed with hence SET, values. This signifies that a greater quantity of pyrolysed
increasing frequency in all samples. SEA was significantly higher in cork within the composite increased its microwave absorbing
all cork-inorganic polymer composites compared to the matrix, ability within the bulk. In the filler material, multiple internal
 R.M. Novais et al. / Construction and Building Materials 229 (2019) 116930
Table 2
Reflection (SER), absorption (SEA), total (SET) and specific (SSE) shielding effectiveness of the geopolymer (GP) matrix and cork-GP composites, all of 3 mm thickness, over the X-
band (8.2–12.4 GHz).
Sample ID SER ( dB) SEA ( dB)
Matrix 2.3–3.4 2.4–2.6
C2.5 2.6–5.2 4.1–4.2
C3.75 2.2–5.2 4.4–4.6
LC2.5_1 2.5–4.1 3.2–3.7
LC3.75_1 2.9–4.8 4.6–4.7
LC2.5_2 2.3–3.5 3.4–3.7
LC3.75_2 2.5–4.6 4.9–5.1
reflection of EM waves occurs at the regularly arranged carbon
honeycomb microstructure which forms an electrically conducting
network. Interestingly, there was little variation in reflection char-
acteristics throughout the samples, since absorption shielding is
the dominant mechanism here. Similar trends were observed in
the 5 and 7 mm thick samples.
The geopolymeric matrix has low attenuation values of 4.7 to
6.1 dB, which compares well to previous reports on the micro-
wave absorption of geopolymers, which showed SET values over
the X-band of around 1 to 5 dB for 1.25 to 4.97 mm thick sam-
ples [42], and similar values for alumino-phosphate geopolymers
[63]. We also measured samples of the geopolymeric matrix made
with just the foaming agents (FA) added, and without pyrolysed
cork, as shown in Fig. 7a. They were actually slightly worse than
the unadulterated matrix, probably because they contained less
mass of the alumino-silicate material in the same volume, and so
had even less absorbing ability.
This suggests that it is the pyrolysed cork additives which have
the major effect on increasing microwave absorption, as was
demonstrated by the results for C2.5 and C3.75 in Fig. 7a and
Table 2. Both show SET significantly larger than the matrix across
the X-band, by a factor of around 50% higher for C2.5, and nearly
60% higher for C3.75. For a conductive honeycomb structure, the
shielding efficiency is given by [64],
SE = 27 al 20logN where l is the length of the waveguide (i.e.,
the length of the honeycomb cell) and a is the radius of the N aper-
tures. Hence, the shielding efficiency increases with increasing
waveguide length over its diameter. Interestingly, natural cork
has a microstructure made of hollow hexagonal honeycomb cells,
whose length (45 lm) is 2–3 times that of their diameter
(15–20 lm). Such structures are likely to have high EMI shield-
ing. Since pyrolysed cork contains honeycombs made of conductive
carbon nanoparticles, they can generate micro-currents inside the
system on exposure to the EM waves, leading to eventual damping
of the incoming wave. Additionally, the porous microstructure
enables EM waves to undergo multiple reflections and consequent
attenuation before passing through the shield. Thus, the unique
microstructure of the cork is supplementing its superior shielding
behaviour.
When 1 or 2 wt% foaming agent was added to C3.75, it made
very little difference to the SET. However, when the foaming agent
was added to C2.5, the values became significantly worse, although
still superior to the matrix (Fig. 7a). This would seem to be related
to the observation made above, that a coarser pore size distribution
was seen with foaming agent added to the composites containing
2.5 wt% pyrolysed cork content than in those with 3.75 wt% cork.
This was attributed to the higher viscosity of the precursor slurry
with more cork preventing bubble/pore growth and coalescence,
resulting in more, and smaller pores with the higher cork content
(Fig. 4). These smaller pores appear to slightly aid absorption in
the X-band, whereas the fewer, larger pores up to 1 mm in size
reduce shielding effectiveness.
7
3 1
SET ( dB) Density (g cm ) SEE ( dB g cm3)
4.7–6.1 1.307 3.7–4.7
6.8–9.3 1.200 5.7–7.8
7.2–9.8 1.180 6.1–8.3
5.8–7.8 0.949 6.2–8.2
7.2–9.5 0.923 6.1–7.7
5.7–7.2 0.745 7.8–10.3
7.4–9.7 0.748 9.9–13.0
When the thickness of the sample was increased to 5 mm and
7 mm, the SET values of all samples increased as the greater bulk
volume increased the ability of the material to absorb microwaves.
As can be seen in Fig. 7b–c, the shielding response became more
irregular, but this was not random noise, as the same minor peaks
and troughs were seen in all samples of the same thickness, even
though these were all individual measurements. Since the filler
material (pyrolysed cork) is electrically conducting, they can gen-
erate micro-currents inside the system on exposure to the EM
waves, leading to eventual damping of the incoming wave. Since
the microstructure of the geopolymer-pyrolysed cork composite
is porous, the variation of micro-current can be very rapid which
was giving rise to fluctuating shielding effectiveness in Fig. 7b–c.
With 5 mm samples, the geopolymer matrix still showed a general
downwards trend with frequency, although the values were
slightly higher (see Table 3). The addition of 2.5 and 3.75 wt%
pyrolysed cork led to increases in SET of between 34 and 60% and
52–87% over the matrix, respectively, and the downwards trend
with increasing frequency had actually become reversed, with a
dip at around 9.5 GHZ but an overall increase with frequency. As
before, LC2.5_1 and LC2.5_2 had worse SET than the C2.5 composite
without foaming agents, but LC3.75_1 and LC3.75_2 were equal
with, or superior-to, C3.75 (Fig. 7b). Similar, but more enhanced,
trends were observed with a thickness of 7 mm (Fig. 7c), for which
all samples, even the geopolymer matrix, showed an overall
increase in SET with frequency. C2.5 had SET between 67 and 72%
higher than the matrix, and C3.75 (with no foaming agent added)
had the greatest SET of all samples, between 104 and 126% greater
than the geopolymeric matrix, at this thickness. The maximum SET
values for each sample are compared in Fig. 7d, and it is clear that
the outstanding composites are those with 3.75 wt% pyrolysed
cork and a thickness of 7 mm, with peak SET values of 14.6 to
15.9 dB.
These values compare well to those of cements and concretes
with similarly low amounts of carbonaceous absorber added.
Cements with 0.6 wt% CNTs added (a much more costly product,
financially and environmentally, than ours) had reflection losses
of around 8 to 10 dB over the X-band for samples between 25
and 25 mm thick, thinner samples giving very uneven MW absorp-
tion through the frequency range [21]. Three centimetre thick con-
crete with 3 wt% CNTs added achieved SET of 12 dB, but only at
frequencies of 2 GHz [27], and 15 wt% CNTs were required to give
SET of 27 dB over the X-band in 2 mm thick Portland cement
composites surpassing the value here reported for the cork-
geopolymer composites, but using a four-times higher carbon
amount [22]. Finite element modelling suggested that a thickness
of 7 cm would be needed to achieve SET values of 20 dB in con-
crete with 3 wt% CNTs added [26], and even then at frequencies
of only 800 MHz. Carbon fibre seems to be more effective than
the use of pyrolysed cork, and 0.5 wt% carbon fibre in 4 mm thick
Portland cement gave SET of 30 dB at low frequencies of 1–
2 GHz [18] and 1.5 wt% gave 40 dB at 1 GHz [20]. A high SET of
8 R.M. Novais et al. / Construction and Building Materials 229 (2019) 116930

Table 3
Minimum and maximum values of total (SET) and specific (SSE) shielding effectiveness of the GP matrix and cork-GP composites with thicknesses of 5 mm and 7 mm over the X-
band (8.2–12.4 GHz) (density as in Table 2).

Sample ID 5 mm thickness 7 mm thickness

1
SET ( dB) SEE ( dB g cm3) SET ( dB) SEE ( dB g 1
cm3)
Matrix 4.6–7.5 3.5–5.7 6.1–7.8 4.7–6.0
C2.5 7.4–9.6 6.2–8.0 10.5–13.0 8.8–10.8
C3.75 8.6–11.4 7.3–9.7 13.8–15.9 11.7–13.5
LC2.5_1 6.1–8.4 6.4–8.9 8.1–10.8 8.5–11.4
LC3.75_1 8.4–10-5 9.1–11.4 12.5–14.6 13.5–15.8
LC2.5_2 6.1–8.5 8.2–7.2 7.8–10.0 8.5–10.5
LC3.75_2 9.1–10.9 12.2–14.6 13.2–14.9 17.6–19.9

26 dB was found for 5 mm thick Portland cement composites list of wastes. Several efforts have been made over the past years
with 0.4 wt% carbon fibre, which was increased to 32 dB when to attempt to valorise this waste stream, including its incorpora-
the fibre was coated with graphene oxide [23], but again this tion in Portland cement [65,66], and its use as soil amendment/fer-
was a vastly more complex and costly process than ours, and still tiliser [67]. Nevertheless, concerns regarding the leaching of trace
involved Portland cement. elements restrict the use of fly ashes as fertilisers [67], while their
Our inorganic polymer composites based on valorising waste alkalis and chloride content [68] is in some cases prohibitive for
materials, were produced simply and easily, and do not release clinker production. Regrettably, the ashes are mostly discarded in
CO2 formation or curing. The only other reported MW absorbing landfills [66,67,69], with associated costs. The landfill tax strongly
geopolymers involve materials made from standard commercial varies within the EU28 from 3 €/ton (in Lithuania) to more than
chemical precursors, not wastes, and the added carbon component 100 €/ton in Belgium (reference year: 2017) [70]. Landfill taxes
is also a non-renewable, commercial product. Alumino-silicate are still expected to rise in the next few years to encourage waste
geopolymer composites with an enormous addition of 14–50 wt% reuse and recycling, but also due to the exhaustion of existing
graphite powder and 5 mm thickness had SET values over the X- landfill space which could be particularly challenging in develop-
band similar to our samples, despite containing up to 20 times ing countries (e.g. India). The latter could be a huge driving force
more carbon [42]. Another article by the same group, on 1–5 mm in the pursuit of novel and environmentally friendlier waste man-
thick alumino-phosphate GP composites with added carbon felt, agement strategies. Taking this into account, it seems a reasonable
also required large amounts of 26–40 wt% carbon to achieve simi- assumption to consider that the pulp and paper industry (producer
lar average SET values of over 10 dB throughout the X-band, and of the biomass fly ash waste) would provide the waste at a lower
only narrow peaks of absorbance reached the high values greater price than that of commercial virgin raw materials (e.g. metakao-
than 20 dB that they reported [63]. lin), which would strongly reduce the geopolymers’ production
Therefore, not only are our sustainable inorganic polymer-cork costs in comparison with the production of geopolymers based
composites produced from wastes equal to any other reported on virgin raw materials [42]. Besides the expected economic
geopolymer MW absorbers over the X-band, but they contain an advantage, our strategy would also mitigate wastes landfilling
order of magnitude less added carbon. In this study, the geopoly- and prevent the depletion of virgin raw materials, in line with
mer was produced using mainly biomass fly ash (70 wt%) as pre- the circular economy concept and contributing towards cleaner
cursor, while in [42] metakaolin was prepared by calcining kaolin production. In fact, the commercial price of their coal fly ash coun-
(at 800 °C for 3 h). This is extremely relevant as it might ensure terpart, which is a by-product not a waste, has been reported to be
lower production costs. In fact, the biomass fly ashes are currently 4 times lower than that of metakaolin [41]. Nevertheless, the eco-
considered a waste (not a by-product), according to the European nomic advantage of the proposed strategy in comparison with

a) GP Matrix b)
C2.5 C3.75
Specific Shielding Efficiency, SSE (-dB g cm )
3

16 5 mm thick
LC2.5_1 LC3.75_1
15
LC2.5_2 LC3.75_2 20
-1

14 18
13 16
SSE (-dB g cm )
3

12 14
11
-1

12
10 10
9 8
8 6
7 4

6 2

5 0
LC2.5_1 3mm
LC2.5_1 5mm
LC2.5_1 7mm
LC2.5_2 3mm
LC2.5_2 5mm
LC2.5_2 7mm
LC3.75_1 3mm
LC3.75_1 5mm
LC3.75_1 7mm
LC3.75_2 3mm
LC3.75_2 5mm
LC3.75_2 7mm
C2.5 3mm
C2.5 5mm
C2.5 7mm
C3.75 3mm
GP 3mm

GP 7mm

C3.75 5mm
C3.75 7mm

4
GP 5mm

3
8 9 10 11 12
Frequency (GHz)

Fig. 8. a) Specific shielding effectiveness (SSE) over the X-band of the matrix and the cork-geopolymer composites for samples 5 mm thick. The maximum SSE value of every
composite sample is compared in b).
 R.M. Novais et al. / Construction and Building Materials 229 (2019) 116930
other literature studies must be supported by a cost-benefit anal-
ysis, and this will be considered in future work. Anyway, a scenario
considering a negative cost for the biomass fly ashes, value
depending on the countries’ landfill tax, when assessing the com-
posites cost, cannot be ruled out, but other factors such as the
transportation costs also need to be accounted for.
Furthermore, the composites made with foaming agents are
also lightweight materials, with densities under 1 g cm 3 (see
Table 2), meaning that they have enhanced specific shielding effec-
tiveness (SSE, in units of dB g 1 cm3). This is significant in applica-
tions where weight is an issue, especially for construction
materials which are, by their nature, reasonably dense. All of the
geopolymers and concrete/cement composites discussed above
will have densities greater than 1 g cm 3, so their SSE values will
be smaller than their SET values. As can be seen in Tables 2 and
3, this is also true for our inorganic polymer-cork composites with-
out added foaming agent (FA), but those with foaming agents
added (1 or 2 wt%) have lower densities, and enhanced SSE values,
particularly for LC2.5_2 and LC3.75_2 with 2 wt% FA added. The
range of SSE values for all samples are shown in Tables 2 and 3,
and the plots of SSE over the X-band for the 5 mm thick samples
are shown in Fig. 8a. The problems of the lower MW absorption
of the lower density composites with 2.5 wt% cork, and larger pore
sizes, means that the advantage of the lower density is not fully
exploited for LC2.5_2, which is no better than the denser
LC3.75_1 at lower frequencies, and significantly worse above
9.5 GHz. However, LC3.75_2 has an SSE much greater than all other
composites, and the difference is even greater with 7 mm thick
composites. The peak SSE values for all composites are shown in
Fig. 8b, and it is apparent how much better the LC3.75_2 samples
are.
4. Conclusions
In this investigation, pyrolysed cork-geopolymer composites
were synthesised and then evaluated, for the first time, as eco-
friendly EMI shielding building materials. Cork is a natural and
highly sustainable material, therefore its incorporation after pyrol-
ysis into geopolymer composites envisioned for EMI shielding
applications, instead of other environmentally unsustainable pre-
cursors (e.g. carbon nanotubes, graphene, carbon fibre), is an envi-
ronmentally friendlier strategy.
Results showed that all cork-geopolymer composites presented
enhanced shielding effectiveness (SET) ability in comparison with
the geopolymer matrix ( 4.7 to 6.1 dB; 3 mm thickness), while
an increase in the pyrolysed cork amount increased the composites
microwave absorbing ability. The maximum SET values over the X-
band ( 13.8 to 15.9 dB) is similar to the only other study on
alumina-silicate geopolymers, despite the much lower amount of
carbon used here (3.75 instead of 40 wt%). Furthermore, the use
of foaming agents effectively reduces the composites density
highly enhancing their SSE (specific shielding effectiveness). The
maximum SSE being 19.9 dB g 1 cm3 for the 3.75 wt% cork-
containing composite.
Declaration of Competing Interest
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared
to influence the work reported in this paper.
Acknowledgements
The authors would like to thank FCT project H2CORK (PTDC/
CTM-ENE/6762/2014), R.M. Novais wishes to thank FCT grant
9
(Ref. CEECIND/00335/2017) and R.C. Pullar wishes to thank FCT
grant IF/00681/2015, for supporting this work. This work was
developed in the scope of the project CICECO - Aveiro Institute of
Materials UID/CTM/50011/2019 (Compete Reference: POCI-01-
0145-FEDER-007679), Associated Laboratory of University of
Aveiro, financed by national funds through the FCT/MCTES. M. Saeli
wishes to thank Portugal 2020 project PROTEUS - POCI-01-0247-
FEDER-017729 co-financed by national funds through the FCT/
MEC. K.P. Surendran acknowledges Indo-Portuguese bilateral pro-
ject (INT/PORTUGAL/P-09/2013) for mutual visits and fruitful
discussions.
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.conbuildmat.2019.116930.
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