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Electromagnetic Shielding Materials in GHz Range

Article in The Chemical Record · January 2018

DOI: 10.1002/tcr.201700066

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Personal Account DOI: 10.1002/tcr.201700066

1
2
3
THE
4
5 CHEMICAL
Electromagnetic Shielding Materials in
6
7
RECORD GHz Range
8
9
10
11 Marta González, Javier Pozuelo, and Juan Baselga*[a]
12
13 This article is dedicated to Prof. Eduardo Ruiz Hitzky in recognition for his work at the
14 time of his retirement.
15
16
17 Abstract: The state-of-the art in the design and the manufacture methods of the different
18 electromagnetic shielding materials has been reviewed. This topic has become a mainstream field
19 of research because of the electromagnetic pollution generated by telecommunication technology
development. The review is centred in absorbent materials and shows a general overview of how
20
the absorption properties of such composites can be tailored through changes in geometry,
21
composition, morphology, and the filler particles content. Although different types of materials
22 are explained, the text is mainly focused on carbon materials such as graphene and carbon
23 nanotubes. In this way, the importance of the dispersion of the conductive fillers in different
24 polymer matrices is discussed. In addition, an extensive study on new complex architectures such
25 as foam-based materials is presented. Finally, the combination of carbon fillers with other
26 constituents such as metallic nanoparticles is mentioned. In all these studies, the efficiency of the
27 composites as absorbent or reflective of electromagnetic radiation is discussed.
28 Keywords: Electromagnetic shielding, Graphene, Carbon nanotubes, Absorbed materials,
29 Conductivity, Pores
30
31
32 and meet the criteria mentioned above is nowadays an active
1. Introduction
33 field of research.
34 With advances in technology, electromagnetic pollution Polymer composites offer several advantages over tradi-
35 appears to be inconvenient because all new electronic equip- tional materials used for electromagnetic interference (EMI)
36 ment and systems emit radiation in the range of microwaves. shielding. Although polymers are electromagnetic transparent,
37 This is why the need to shield such radiation arises. different strategies are available to convert them into active
38 Interaction of electromagnetic waves from different sources electromagnetic shields. The incorporation of nanomaterials,
39 may result in device malfunction. such as nanocarbons and magnetic nanoparticles, into a
40 Shielding materials must meet a series of requirements to polymeric matrix is becoming one of the most effective
41 satisfy current demands: chemical and corrosion resistance, method to achieve this end.
42 lightweight, flexibility, tuneable morphology, processing easi- The EMI can leave or affect an electronic circuit in two
43 ness and inexpensiveness. The fabrication of materials which ways: radiated or conducted. Conduction coupling of EM
44 are capable of shielding incident electromagnetic radiation signals can be prevented by the circuit design and using
45 frequency filters or inductors. Radiation on the other
46 hand, can be avoided by isolating the source with a
47 [a] M. González, J. Pozuelo, J. Baselga physical shield. EMI shielding is thereby dedicated to
48 Departmento de Ciencia e Ingenierı́a de Materiales e Ingenierı́a suppress or attenuate EM radiation from emitters with
49 Quı́mica (IAAB) materials that are able to interact with those signals. At the
Universidad Carlos III de Madrid
50 Avda. de la Universidad, 30 (28911) present time, new EM shielding and absorbing materials
51 Leganés, Madrid, Spain have been designed and synthesized to reduce the fault
52 E-mail: jbaselga@ing.uc3m.es probability of electronic equipment caused by the EM

Chem. Rec. 2018, 18, 1 – 11 © 2018 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim Wiley Online Library 1
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1 noise and pollution. In the present work we will focus on

2 microwave radiation.
3 When an electromagnetic wave with an incident energy
4 (EI) impacts on a material (Figure 1) two waves are created on
5 the surface: A reflected wave (ER), due to the impedance
6 mismatch between the two mediums, and a transmitted wave
7 into the material (EI-R). Inside the material, a fraction of the
8 wave (EI-R) may be dissipated as heat (EA) by Joule effect until
9 it reaches the second surface of the material. At this point,
10 two new waves appear: One that is transmitted through the
11 surface (ET) and a new wave that is reflected into the material.
12 This process is repeated successively until it meets the criteria
13 stated by equation (1):
14 X X X
15 EI ¼ ER þ EA þ ET ð1Þ
16
17 Both in the reflection and transmission process, waves
18 generated at each step, may cause constructive and destructive
Figure 1. Attenuation mechanisms of the incident electromagnetic radiation.
19 interferences depending on the sample thickness and fre-
20 quency.
       
21 The reflection process on each plane of the material is h d 2d
SE ¼ 20log þ 20log exp þ 20log 1  exp
22 what is called multiple reflections. Therefore, the electro- 4h0 d d
23 magnetic shielding efficiency of a material can be quantified ð3Þ
24 as the sum of three contributions: reflection, absorption and
25 multiple reflections. where the skin thickness is defined as the depth at which the
26 field decreases to 1/e from its initial value and is a function of
27 SE ¼ SE R þ SE A þ SE MR ð2Þ frequency (f ), permeability (m) and conductivity (s) as shown
28 in eq. (4):
The electromagnetic shielding efficiency can be expressed
29
as a function of: impedance mismatch between the medium d ¼ ðpf msÞ1=2 ð4Þ
30
and the material (h0 and h respectively); sample thickness (d)
31
and skin thickness (d):
32
33
34
35
36 Ms. M. González currently collaborates as Prof. J. Baselga, head of the Polymer and
37 PhD student in the Polymer and Compo- Composites group at UC3M.
38 sites group at UC3M.
39
40
41
42
43
44 Dr. J. Pozuelo is staff member of UC3M
45 and collaborates in the Polymer and
46 Composite group.
47
48
49
50
51
52

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1 The impedance can be expressed as the ratio between the electromagnetic wave can couple to a material and dissipate the
2 electric and magnetic fields, where j accounts for an electromagnetic energy. The main loss mechanisms for non-
3 imaginary value and e for the complex permittivity: magnetic materials are dipolar losses (for dielectric insulators)
4  1=2 and conduction losses (mainly in metals and highly conductive
5 jE j j2pf m materials). Magnetic materials also exhibit additional magnetic
h¼ ¼ ð5Þ
6 jHj s þ j2pf e losses such as hysteresis, domain wall resonance and electron
7 spin resonance apart from conduction losses.
8
If the conductivity of the propagation medium is zero
9
(s = 0) and the conductivity in the conductive material is s
10
(@ 2pfe), equation 5 can be simplified as: 2. Electromagnetic Shielding Materials
11  1=2  
m0 2pf m 1=2 2.1. Electric Materials
12 h0 ¼ and h0 ¼ ð6Þ
e0 s
13 In electric materials, absorption is related to their complex
14 where the 0 index stands for the values in free space. Multiple permittivity (e) and the loss tangent (tand). Complex
15 reflections can be neglected when the sample thickness is permittivity is the physical property that describes the
16 bigger than the skin thickness. In this case, the absorbed interaction between matter and electromagnetic fields, and it
17 radiation is high enough so that those constructive and is related to the structural and physico-chemical properties.
18 destructive interferences cannot be produced, and only two 0 00

19 er ¼ e  je ð10Þ
mechanisms are possible in the electromagnetic shielding
20 process: reflection and absorption. Taking this into account,
21 The complex permittivity measures the ability of a
and using equations 4 and 6, the electromagnetic shielding material to absorb and store potential electrical energy and is
22 (equation 3) can be expressed as:
23 composed of a real permittivity (e’) part, that describes the
   ability of a material to store energy when it is subjected to an
24 s  
SE ¼ 39:5 þ 10log þ 8:7d ðpf msÞ1=2 ð7Þ electric field and influences the electric field distribution and
25 2pf m
26 the phase of waves travelling through the material, and an
27 Electromagnetic shielding can be determined from the imaginary permittivity (e’’) part, that influences both energy
28 reflection (R), absorption (A) and transmission (T) coeffi- absorption and attenuation and describes the ability to
29 cients as a function of the reflected, transmitted and incident dissipate energy in response to an applied electric field
30 powers (PR, PT and PI, respectively), and therefore: through various polarization mechanisms that commonly
00
31
PR P result in heat generation.[2] Loss tangent ðtand ¼ e =e0 Þ
32 R¼ ; T ¼ T ; A ¼ 1  ðR þ T Þ ð8Þ indicates the ability of the material to transform energy into
PI PI
33 heat.
34 In this way, the electromagnetic shielding can be expressed
35 as: For obtaining good dissipation of the energy by Joule
36 effect, it is necessary that shields have good thermal
     
37 1 1 1R conductivity. When microwaves penetrate and propagate
SE ¼ 10log ; SE R ¼ 10log ; SE A ¼ 10log ð9Þ
38 T 1R T through a dielectric material the internal field generated
39 within the affected volume induces translational motions of
40 Reflection is the first mechanism that occurs when an free or bound charges such as electrons or ions, and rotates
41 electromagnetic wave reaches the first incident plane of a shield. charge complexes such as dipoles. Inertial, elastic and
42 Reflection peaks when the impedance of the electromagnetic frictional forces resist these induced motions and cause losses,
43 wave is higher than the impedance of the shield. For this reason a consequence of which is volumetric heating.[3]
44 and according to the equations (3), (5) and (6) the shield has to
45 be electrically conducting (resistivity values of 1 W·m are
typically sufficient).[1] For composites which contain conductive 2.2 Magnetic Materials
46
47 fibres, the percolation threshold must also be reached since the In an analogous way to the electric losses, the losses that occur
48 conduction requires connectivity in the conduction path. The due to a time varying magnetic field can be described by a
49 most used shields for reflective applications have been metals, complex relative permeability:
50 where the presence of free electrons causes reflection.
0 00

51 The second term of the equation (3) is related with the mr ¼ m  im ð11Þ
52 absorption. There are different mechanisms by which the

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1 Table 1. EMI shielding efficiency of polymer composites with different CNTfiller content.
2
Matrix Filler content d (mm) s(S/m) SET (dB) Ref.
3
4 PU 22 wt.% CNT 0.1 5 20 [5]
5 PU 10 wt.% MWCNT > 0.2 12.4 29 [6]
PU 5 wt.% SWCNT 2 100 22 [7]
6
PU 10 wt.% MWCNT 2.5 790 41.6 [8]
7 PU/PEDOT 30 wt.% MWCNT 2.5 275 45 [9]
8 PU 76 wt.% CNT 1 2100 80 [10]
9 PU 10 wt.% CNT 2 N/A 5 [11]
10 Cellulose 9.1 wt.% CNT 0.2 375 20 [12]
PS 15 wt.% CNT N/A 0.1 19 [13]
11
PMMA 40 wt.% MWCNT 0.06–0.165 3000 27 [14]
12 PMMA 10 vol % MWCNT 2.1 150 40 [15]
13 Epoxy 15 wt.% SWCNT 1.5 15 30 [16]
14 PC 15 wt.% MWCNT 6 1000 28 [17]
15 PTT 10 wt.% MWCNT 1.5–2 30 42 [18]
PVDF 3.5 wt.% CNT 1.1 100 17.7 [19]
16 UHMWPE 10 wt.% CNT 1 100 50 [20]
17 PEDOT 15 wt.% CNT 2.8 1935 58 [21]
18 HDPE 18 wt.% MWCNT 3 1000 58 [22]
19 PE 5 wt.% CNT 2.1 80 46.4 [23]
PANI 2 wt.% CNT N/A 0.006 20 [24]
20
PANI 1 wt.% CNT N/A 14 19.4 [25]
21 PANI 10 wt.% CNT N/A 2950 98 [26]
22 ABS 10 wt.% CNT N/A 105 39 [27]
23
24
0 00
25 In which m is the permeability and m describes the However, if the shield is thinner than the skin depth, the
26 magnetic losses. An analogous magnetic loss tangent, tandm influence of multiple-reflection will be significant in decreas-
ing overall EMI shielding.[29] Increasing the frequency, the
00
27
can also be defined where (tandm ¼ m =m0 Þ.
28 current in the conductor flows more and more on the surface
29 For magnetic materials the loss tangent can be expressed of the conductor.
30 in terms of three main contributors:
31
tandm ¼ tandh þ tande þ tandr ð12Þ 3. Conductive Fillers in Polymer Composites
32
33 Generally, polymer composites contain conductive fillers such
34 where tandh , tande and tandr are the hysteresis, eddy current as metal or magnetic nanoparticles, carbon-based materials
35 and ‘residual’ loss tangent respectively. (carbon nanotubes (CNT), graphene (Gr), carbon black and
36 As a result of hysteresis, energy in a magnetic material is graphite) which are the most reported lately due to their
37 dissipated as heat through the B-H loop. lightweight and good EMI SE. The EMI shielding of a
38 For high conductivity materials such as metals or for very composite shielding material depends mainly on the aspect
39 large samples, where the skin depth is less than the ratio of fillers, filler’s intrinsic conductivity, dielectric con-
40 dimensions of the sample, the influence of eddy currents on stant, magnetic properties and physical geometry.[30] A wide
41 the magnetic field ceases to be negligible. In this situation, a range of values for EMI SE and conductivities of different
42 broad range of spin waves are excited, as opposed to only the composites have been reported in the literature over the last
43 uniform precession with the result that in metals the eddy decades, depending greatly on the processing method,
44 current process often dominates. polymer matrix and carbonaceous material type (Table 1 and
45 The third term of the equation (3) is related with the 2).
46 multiple reflections. The factor SEMR of the equation (2) is As a general trend, it can be observed that the addition of
47 usually only important when metals are thin and at low carbon nanotubes increases the conductivity and SE in the
48 frequencies (i. e.,below approximately 20 kHz).[4] composites at the same frequency value. Jia et al.[23] stated
49 Their negative contribution to global shielding (SEMR) that to obtain 20 dB (the minimum commercially acceptable
50 can be neglected when the thickness of the shield is greater EMI SE) a minimum conductivity of at least 1 S/m is
51 than depth of penetration of the wave (d) or when (SEA) is necessary. It is worth mentioning that the thickness of the
52 higher than 10 dB according to the Schelkunoff ’s theory.[28] sample is an important factor to consider,[22] as thicker

Chem. Rec. 2018, 18, 1 – 11 © 2018 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim Wiley Online Library 4
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1 Table 2. EMI shielding efficiency of polymer composites with different graphene filler content.
2
Matrix Filler content d (mm) s(S/m) SET (dB) Ref.
3
4 PU 10 wt.% Gr 2 N/A 5 [11]
5 PU 0.12 vol. % Gr 0.05 3500 14 [32]
epoxy 15 wt.% Gr N/A 10 21 [16]
6
epoxy 2 wt.% Gr N/A 1 38 [33]
7 PANI 0.15 wt.% Gr 2.5 N/A 45.1 [34]
8 PANI 1 wt.% Gr N/A 930 24.3 [25]
9 PEI 6 vol % Gr 2.3 10-3 44 [35]
10 PVDF 0.5 wt .% Gr N/A 10-4 20 [36]
PVDF-HFP 40 wt.% Gr N/A N/A 30 [37]
11
P3HT 90 wt.% Gr 2 9000 > 40 [38]
12
13
14 samples would display higher EMI SE, as shown in equation polymer matrices. As an example, Bhattacharya et al. have
15 3. According to Pande et al.[14] multiple laminated composites demonstrated the higher efficiency of graphene sheets
16 exhibit higher absorption capacities than bulk composites, compared to carbon nanotubes when dispersed in polyur-
17 due to internal reflections taking place between the bounda- ethane (8 dB vs. 5 dB at 10 wt% carbon filler loading).[11] In
18 ries of each layer. This effect can be compared to the effect another work, Chen et al. have reported the electric con-
19 found on Salisbury screens. ductivity and the EMI SE of polyaniline composites
20 EMI SE and conductivity are affected greatly by the containing SWCNT, graphite nanosheets (GNS) or hybrid
21 processing techniques used. In this respect, Al-Saleh et al[20] fillers.[25] The composites were prepared by polymerization
22 compares various processing techniques and concludes that in situ. The conductivity of the composites was 14 S/m and
23 the best processing method to obtain the highest EMI SE 930 S/m by adding 1 wt% of SWCNT and GNS respectively.
24 value is by melt mixing.[31] This technique is better than While the hybrid composite with 1 wt% SWCNT/GNS
25 solution processing[31] while this latter is better than wet shows a very high value of conductivity (1620 S/m). The
26 mixing.[20] The reason why melt mixing seems to give better values of SET were 19.4, 24.3 and 27 dB for samples with
27 results over the other techniques is due to the carbon 1 wt% SWCNT, GNS and hybrid nanocomposites respec-
28 nanotubes being localized in the external surface of large tively which make this latter an excellent candidate as EM
29 polymer particles. shielding material.
30 Another factor that affects the EMI SE is the CNT
31 length. In this regard, various works demonstrated that the
4. Foam-Based Materials
32 longer the CNT the better the conductivity and thus the EMI
33 SE, as reported by Gupta et al.[6] and Huang et al.[16–39] This As discussed above, an increase in conductivity implies an
34 is due, to the higher aspect ratio (L/d) found in the longer increase in both reflection and absorption losses. Let us
35 CNT. They found that the percolation threshold seems to consider the following equation that describes the reflection
36 occur at lower weight fractions as CNT longitude increase. coefficient at an interface:
37 The main types of carbon nanotubes used are single
hM  ho
38 walled carbon nanotubes (SWCNT) and multi walled carbon r¼ ð13Þ
hM þ ho
39 nanotubes (MWCNT). CNT type also seems to influence the
40 EMI SE parameters since the greater number of defects where r is the reflection coefficient and h the impedance of
41 present in MWCNT increases their permittivity. This makes the propagating medium. The reflection coefficient falls to
42 MWCNT advantageous for EMI SE where the main zero when hM ¼ ho , i. e., when the impedance in the material
43 shielding mechanism is absorption.[22] first layer matches the incident medium impedance. In this
44 Alignment of nanotubes is another factor that has a great context, nowadays porous materials are widely used to
45 effect in the electrical properties of the composites and their minimize the impedance mismatch and the reflection
46 percolation threshold.[40] When the nanotubes have a high coefficient. To comply with this end, a highly porous outer
47 orientation and are aligned, there are fewer contacts between surface with a pore size like the incident radiation would be
48 the tubes, and as a consequence, reduces the electrical required. In principle, when radiation interacts with the
49 conductivity and increases the percolation thresholds as surface of a porous conductive material, it becomes
50 compared to randomly oriented CNT. distributed among the pores and their walls. The major
51 Besides, the filler type effect has been studied by different portion of the reflected radiation will arise from reflections
52 authors by adding different doping materials to the same

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1 values up to 80 dB in the K-band at very low content of

2 MWCNT (0.25 vol %). Subsequently, they used a precipitation-
3 polymerization technique to prepare MWCNT/ PMMA foams.
4 This method allowed to obtain better MWCNT dispersions
5 improving thus the conductivity and EMI SE values. Addition-
6 ally, the absorbed power was higher than 90 % for composites
7 with only 2 wt.% MWCNT prepared by precipitation-polymer-
8 ization.[44] In another work, MWCNT/PC composites were
9 prepared by melt-extrusion and compression and expanded by
10 supercritical CO2; they found that limiting the diffusion time of
11 CO2 inside the material, it was possible to obtain foams with a
12 gradient morphology which were capable of absorbing up to
13 90 % of the incident radiation.[45,46]
14 Graphene has been also used as conductive filler. For
15 example, Zhang et al. reported the preparation of graphene/
Figure 2. Dissipation of the energy in foam-based materials.
16 PMMA composites by solution blending method using
17 supercritical CO2 as foaming agent.[47] Many other techniques
18 have been used to prepare porous graphene-polymer compo-
19 originated at the pore walls, since reflections from the inner sites. Polyimide composites foams with reduced graphene
20 part of the pores can be neglected (Figure 2). Therefore, oxide (rGO) have been fabricated via a three-step method:
21 tailoring the fraction and size of pores created on the surface in situ polymerization, nonsolvent induced phase separation
22 of a conductive compound will help to modulate the and thermal imidation.[48] Similarly, porous PS/graphene
23 phenomenon of electromagnetic reflection. Minimizing composites have been prepared using a combination of high-
24 reflection, a larger fraction of the radiation will penetrate into pressure compression moulding plus salt-leaching.[49] More-
25 the material, being able to dissipate it by absorption.[41] over, lightweight microcellular polyetherimide (PEI)/graphene
26 nanocomposite foams have been synthesized using water
27 vapour induced phase separation (WVIPS). However, in
4.1. Polymer-Based Foams with Carbonaceous Fillers
28 comparison with carbon nanotube fillers, higher amounts of
29 To further reduce reflections of the polymer composites graphene filler are required to obtain polymer/graphene
30 discussed above, polymer composite foams are suitable candi- systems with good EMI SE values. These results suggest that
31 dates. These compounds can be formed easily following various CNTs are more efficient than graphene because of their high
32 techniques: supercritical CO2 drying or expansion, use of aspect ratio, better interaction with the matrix, lower
33 chemical foaming agents, induction of phase separation proc- percolation threshold and higher conductivity values.
34 esses, etc.
35 These systems were first reported by Yang et al. comparing
4.2. Metal-Based Foams
36 PS foams filled with carbon nanofibers[13] and carbon nano-
37 tubes.[42] Yang synthesized porous composites using the Metal-based materials are by far the most common materials for
38 foaming agent technique (AIBN) and obtaining pore sizes EMI shielding due to their high electrical conductivity and good
39 between 40 and 170 mm. The authors proved that CNT were mechanical properties.[50] However, the high weight of them
40 more efficient than nanofibers thanks to their high aspect limits their use in some applications. Metal foams are currently
41 ratio: less amount of CNT is enough to get the required value the focus of much research because of their lightweight, stiffness,
42 for a commercial shielding material (20 dB). strength, and high electrical and thermal conductivity.[51] Metal
43 Thomassin et al. have been working extensively on the foams with different specific physical properties can be produced
44 minimization of the reflections in the K-band frequency range on demand, varying cell topology (open or closed cells), material
45 using CNT/polymer foams expanded by the supercritical CO2 (aluminium, copper, titanium etc.), apparent density, and pore
46 method. In their first work, they prepared nanocomposite foams size. In this way, the most appropriate foams can be tailored to
47 of polycaprolactone (PCL) with MWCNT as fillers.[43] Two meet specific engineering design applications. Titanium foams
48 techniques were used for the preparation of the composites: melt have been prepared using different synthesis methods such as
49 blending and co-precipitation. Complied results of conductivity polymer impregnation[52] or the use of different evaporative
50 and EMI SE show that the latter is more efficient than the types of space holders (acrowax, ammonium bicarbonate).[53]
51 former, because the original length of CNT was better preserved Titanium foam exhibits an EMI SE around 45 dB in the GHz
52 better co-precipitation method. Besides, samples presented SET range with 87–89 % porosity and a pore size between 1.0 and

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1 3.0 mm. Xu et al.[54] prepared aluminium foams with different the pore size and stabilizing the scaffold’s structure. To control
2 porosity values using a melt foaming method. The authors the pore size and to obtain hierarchical pore morphology
3 reported good EMI SE (25–65 dB) in the GHz range which (Figures 3b and 3d) a modified version of a previously reported
4 increased with increasing porosity (77–93 %.) and the pore size hydrothermal method[60] was used. This method involved the
5 (4.3–7.9 mm). preparation of stable aqueous emulsions of graphene oxide
6 containing hexane droplets and a subsequent careful cold
7 evaporation of hexane followed by lyophilisation of the aqueous
4.3. Carbon-Based Foams
8 phase. The growth of the ice crystals displaced and compressed
9 In the previously cited polymer composites, individual con- the CNT-rGO towards the walls of the scaffold achieving more
10 ductive carbon-based fillers are randomly distributed inside the consistent structures and increasing the CNT connectivity and,
11 polymer and the electrical conductivity of these composites consequently, the conductivity of the material.
12 strongly relies on the percolation threshold. As a result, a high Therefore, the absorbed power in the GHz range was
13 content and good dispersion of carbon-based fillers are usually significantly greater (close to 80 % of incident power) than
14 required to form a conductive interconnected network in the the power reflected (close to 20 % of incident power).
15 insulating polymer matrix to improve the electrical conductivity High-performance EMI shields based on rGO and poly-
16 and hence the EMI SE of the composites.[39,55–57] Here appear styrene were obtained via high-pressure solid-phase compression
17 carbon-based foams as good candidates to further reduce the moulding. The morphology of these structures showed the
18 weight of the targeted shielding composites. There are different selective distribution of rGO among PS domains. The SET value
19 synthesis methods to prepare these structures. For instance, of the composite with 3.47 vol % rGO was 41.4 dB but the
20 carbon nanotube scaffolds can be easily prepared using freeze- contribution of the absorption to the total EMI SE was more
21 drying protocol of CNT aqueous dispersions with chitosan as a dominant (97 %). This was because the graphene sheets were
22 binder. The porosity of these scaffolds can be controlled varying compressed in the walls forming a network around the PS
23 the freezing rates (20–150 mm) as shown in the Figures 3a and particles; this structure behaves just like the foams minimizing
24 3b. Samples with the highest pore size and porosity present the reflection of the electromagnetic wave.[61] Similarly, Yan et al.
25 lower reflected power and higher absorbed power (about 70 %). have utilized the same method to prepare reduced graphene
26 These structures prepared with different CNT percentages (3– oxide/ultrahigh molecular weight polyethylene (UHMWPE).[62]
27 7 wt. %) exhibit a EMI SE of 14–35 dB in the frequency range The morphology is similar to that reached using PS matrix, an
28 8–18 GHz.[58] In another work, graphene and graphene/CNT interconnected network of rGO forming the walls around the
29 hybrid foams with controlled porosity via a modified hydro- UHMWPE core. The composites present a very high SET of
30 thermal method (HT) have been successfully prepared.[59] In this 32.4 dB at a low rGO content of 0.66 vol % and an electrical
31 shielding material, the dielectric is substituted by graphene conductivity of 3.4 S/m.
32 which acts as the CNT binder and as a surfactant controlling
33
5. Magnetic Nanoparticles Inclusions
34
35 For absorbing applications in high frequency range (in the
36 GHz range), magnetic metallic materials were considered
37 good candidates since the shielding should satisfy the
38 impedance matching condition mr=e  1, making magnetic
r
39
and dielectric properties essential for a good absorber.
40
Nevertheless, the relative complex permeability of magnetic
41
metallic materials decreases due to eddy currents induced by
42
electromagnetic waves.[63] Thus, it may be better to use
43
isolated metallic particles having sizes smaller than the skin
44
depth of electromagnetic waves.[64] The microwave absorption
45
of magnetic nanoparticles is caused mainly by ferromagnetic
46
resonance which is a precession of magnetization (M) around
47
the anisotropy field. In the case of a ferromagnetic material
48
with a uniaxial magnetic anisotropy, the direction of magnet-
49
ization is restricted around the magnetic easy-axis. Super-
50
paramagnetic nanoparticles have a small coercitivity value
51 Figure 3. CNT foams prepared by slow (a) and fast (b) freezing. Hierarchical
pore morphology in graphene/CNT hybrid foams (c and d). which improves the permeability and therefore the magnetic
52

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1 Table 3. EMI SE of polymer nanocomposites with different carbonaceous constituents and magnetic NPs.
2
Carbonaceous constituent Magnetic NPS Matrix SET (dB) Reference
3
4 MWCNT g-Fe2O3 PANi 34.1 [70]
5 MWCNT Fe3O4 wax 75 [71]
6 MWCNT Fe3O4 PANi/wax 16 [71]
7
MWCNT rGO-MnFe2O4 PVDF 38 [72]
MWCNT Fe3O4 PC/SAN 32.5 [73]
8 SWCNT Co/Ni – 24 [63]
9 Graphene Fe3O4 PANi 26 [74]
10 rGO g-Fe2O3 PANi 51 [75]
11 rGO Fe3O4 – 41 [76]
12 rGO Fe3O4 PS 30 [77]
13 Graphene Fe3O4 PEI 41.5 [78]
Graphene Ag/Ni PANi 29.33 [79]
14 GO Ferrofluid cement 46 [80]
15 GO/MWCNT Ni PE/PEO > 25 [81]
16 Carbon nanofiber Fe3O4 epoxy 20 [82]
17 Carbon nanofiber Fe3O4 PDMS 67.9 [83]
18
19
20 loss. When introducing magnetic nanoparticles in a material, materials with high-performance and the maximum miniatur-
21 both complex permittivity and complex permeability increase. ization. In order to make an efficient shield it must exhibit
22 The increase of the former is due to the existence of multiple moderate electrical conductivity. The most studied materials
23 dielectric relaxations in the magnetic nanocomposites. Thus for absorption applications are composites formed by
24 the impedance matching performance of these composites is conductive fillers in polymeric matrix and based-foam
25 improved, which increase the absorption ability.[65] For this materials. The morphology of the foams allows minimizing
26 reason, magnetic nanoparticles have been incorporated to the electromagnetic wave losses by reflection increasing, on
27 composites in order to improve the shielding efficiencies. the other hand, the absorption capacity. Furthermore, the
28 Although some studies have been carried out incorporating incorporation of magnetic nanoparticles to these materials
29 only magnetic particles to polymer matrices,[66–69] the majority seems to be an interesting field of research because the
30 of the investigations are focused to verify the extraordinary synergistic effect of magnetic NPs and electric fillers may
31 combination and synergistic effect between carbonaceous improve the EMI SE. Although different strategies and
32 constituents and magnetic nanoparticles; Table 3 compiles the considerable amount of work have been done to make
33 most relevant works in these materials. different types of nanocomposites for EMI shielding, still
34 In general, it should be noted that the incorporation of many researchers are working in this field to achieve good
35 magnetic nanoparticles enhances strongly the polarization shielding depending upon the particular applications.
36 and the magnetic loss, which in turn results in a good
37 shielding behaviour. The interfacial polarization in the
Acknowledgements
38 magnetic clusters contributes to the absorption-dominant
39 shielding mechanism which was explained using resistor This work was supported by grants NANOARQ (MAT2014-
40 capacitor circuit model. The combination of conductive fillers 57557-R) from the Spanish Ministerio de Ciencia y
41 and magnetic nanoparticles in electrical contact seems to have Tecnologı́a.
42 a synergistic effect on the shielding efficiency, yielding higher
43 values than composites without magnetic NPs. Finally, we
44 should mention that decoration of nano-conductive fillers References
45 with magnetic nano-particles may be a suitable route to
46 obtain materials with improved shielding properties. [1] D. D. L. Chung, J. Mater. Eng. Perform. 2000, 9, 350–354.
[2] D. El Khaled, N. Novas, J. A. Gazquez, R. M. Garcia, F.
47
Manzano-Agugliaro, Fruit and Vegetable Quality Assessment via
48
6. Summary Dielectric Sensing, 2015.
49 [3] W. H. Sutton, Mat. Res. Soc. Symp. Proc. 1992, 269.
50 This paper offers a perspective on the experimental efforts [4] X. C. Tong, Interference Shielding, CRC Press, 2009.
51 towards the development of new electromagnetic shields that [5] A. S. Hoang, Adv. Nat. Sci. Nanosci. Nanotechnol. 2011, 2,
52 fulfil the required criteria to manufacture lightweight 025007.

Chem. Rec. 2018, 18, 1 – 11 © 2018 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim Wiley Online Library 8
 Pe r s o n a l A c c o u n t THE CHEMICAL RECORD

1 [6] T. K. Gupta, B. P. Singh, S. R. Dhakate, V. N. Singh, R. B. [34] H. Yu, T. Wang, B. Wen, M. Lu, Z. Xu, C. Zhu, Y. Chen, X.
2 Mathur, J. Mater. Chem. A 2013, 1, 9138. Xue, C. Sun, M. Cao, J. Mater. Chem. 2012, 22, 21679.
3 [7] Z. Liu, G. Bai, Y. Huang, F. Li, Y. Ma, T. Guo, X. He, X. Lin, [35] J. Ling, W. Zhai, W. Feng, B. Shen, J. Zhang, W. G. Zheng,
4 H. Gao, Y. Chen, J. Phys. Chem. C 2007, 13696–13700. ACS Appl. Mater. Interfaces 2013, 5, 2677–2684.
[8] T. K. Gupta, B. P. Singh, S. Teotia, V. Katyal, S. R. Dhakate, [36] V. Eswaraiah, V. Sankaranarayanan, S. Ramaprabhu, Macromol.
5
R. B. Mathur, J. Polym. Res. 2013, 20, 32–35. Mater. Eng. 2011, 296, 894–898.
6
[9] M. Farukh, R. Dhawan, B. P. Singh, S. K. Dhawan, RSC Adv. [37] P. Kumar, A. Kumar, K. Y. Cho, T. K. Das, V. Sudarsan, AIP
7 Adv. 2017, 7, DOI 10.1063/1.4973535.
2015, 5, 75229–75238.
8 [38] M. Fang, Z. Y. Tang, H. B. Lu, S. Nutt, J. Mater. Chem. 2012,
[10] Z. Zeng, M. Chen, H. Jin, W. Li, X. Xue, L. Zhou, Y. Pei, H.
9 Zhang, Z. Zhang, Carbon N. Y. 2016, 96, 768–777. 22, 109–114.
10 [11] C. K. Das, P. Bhattacharya, S. S. Kalra, J. Mater. Sci. Res. [39] N. Li, Y. Huang, F. Du, X. He, X. Lin, H. Gao, Y. Ma, F. Li,
11 2012, 1, p126. Y. Chen, P. C. Eklund, Nano Lett. 2006, 6, 1141–1145.
12 [12] E. S. M. Imai, K. Akiyama, T. Tanaka, Environ. Sci. Technol. [40] M. Arjmand, T. Apperley, M. Okoniewski, U. Sundararaj,
13 2010, 70, 1564–1570. Carbon N. Y. 2012, 50, 5126–5134.
14 [13] Y. Yang, M. C. Gupta, K. L. Dudley, R. W. Lawrence, Adv. [41] M. González, G. Mokry, M. de Nicolás, J. Baselga, J. Pozuelo,
Mater. 2005, 17, 1999–2003. Carbon Nanotub. – Curr. Prog. their Polym. Compos. 2016, 1–
15
[14] S. Pande, B. P. Singh, R. B. Mathur, T. L. Dhami, P. Saini, 26.
16
S. K. Dhawan, Nanoscale Res. Lett. 2009, 4, 327–334. [42] Y. Yang, M. C. Gupta, K. L. Dudley, R. W. Lawrence, Nano
17
[15] H. M. Kim, K. Kim, S. J. Lee, J. Joo, H. S. Yoon, S. J. Cho, Lett. 2005, 5, 2131–2134.
18 [43] J.-M. Thomassin, C. Pagnoulle, L. Bednarz, I. Huynen, R.
S. C. Lyu, C. J. Lee, Curr. Appl. Phys. 2004, 4, 577–580.
19 Jerome, C. Detrembleur, J. Mater. Chem. 2008, 18, 792.
[16] J. Liang, Y. Wang, Y. Huang, Y. Ma, Z. Liu, J. Cai, C. Zhang,
20 [44] J. M. Thomassin, D. Vuluga, M. Alexandre, C. Jérôme, I.
H. Gao, Y. Chen, Carbon N. Y. 2009, 47, 922–925.
21
[17] A. P. Singh, B. K. Gupta, M. Mishra, Govind, A. Chandra, Molenberg, I. Huynen, C. Detrembleur, Polymer (Guildf).
22 2012, 53, 169–174.
R. B. Mathur, S. K. Dhawan, Carbon N. Y. 2013, 56, 86–96.
23 [45] L. Monnereau, L. Urbanczyk, J.-M. Thomassin, M. Alexandre,
[18] A. Gupta, V. Choudhary, Compos. Sci. Technol. 2011, 71,
24 C. Jérôme, I. Huynen, C. Bailly, C. Detrembleur, Polymer
1563–1568.
25 (Guildf). 2014, 55, 2422–2431.
[19] M. Arjmand, U. Sundararaj, Compos. Sci. Technol. 2015, 118,
[46] L. Monnereau, L. Urbanczyk, J.-M. Thomassin, T. Pardoen,
26 257–263.
C. Bailly, I. Huynen, C. Jérôme, C. Detrembleur, Polymer
27 [20] M. H. Al-Saleh, Synth. Met. 2015, 205, 78–84.
(Guildf). 2015, 59, 117–123.
28 [21] M. Farukh, A. P. Singh, S. K. Dhawan, Compos. Sci. Technol.
[47] H. Zhang, Q. Yan, W. Zheng, Z. He, Z. Yu, ACS Appl. Mater.
29 2015, 114, 94–102.
Interfaces 2011, 3, 918–924.
30 [22] Y.-J. Yim, S.-J. Park, J. Ind. Eng. Chem. 2015, 21, 155–157.
[48] Y. Li, X. Pei, B. Shen, W. Zhai, L. Zhang, W. Zheng, RSC Adv.
31 [23] L.-C. Jia, D.-X. Yan, C.-H. Cui, X. Jiang, X. Ji, Z.-M. Li, J.
2015, 5, 24342–24351.
Mater. Chem. C 2015, 3, 9369–9378. [49] D.-X. Yan, P.-G. Ren, H. Pang, Q. Fu, M.-B. Yang, Z.-M. Li,
32
[24] H. M. Kim, K. Kim, C. Y. Lee, J. Joo, S. J. Cho, H. S. Yoon, J. Mater. Chem. 2012, 22, 18772.
33
D. a. Pejaković, J. W. Yoo, a. J. Epstein, Appl. Phys. Lett. 2004, [50] B. P. Singh, K. Saini, V. Choudhary, S. Teotia, S. Pande, P.
34
84, 589. Saini, R. B. Mathur, J. Nanopart. Res. 2014, 16, DOI
35 [25] Y. J. Chen, N. D. Dung, Y. A. Li, M. C. Yip, W. K. Hsu, 10.1007/s11051-013-2161-9.
36 N. H. Tai, Diamond Relat. Mater. 2011, 20, 1183–1187. [51] L. T. L. Catarinucci, G. Monti, Prog. Electromagn. Res. B 2012,
37 [26] T. K. Gupta, B. P. Singh, R. B. Mathur, S. R. Dhakate, 45, 1–18.
38 Nanoscale 2014, 6, 842–851. [52] P. S. Liu, H. B. Qing, H. L. Hou, Y. Q. Wang, Y. L. Zhang,
39 [27] J. Jyoti, S. Basu, B. P. Singh, S. R. Dhakate, Composites Part B Mater. Des. 2016, 92, 823–828.
40 2015, 83, 58–65. [53] D. P. Mondal, M. Patel, S. Das, a. K. Jha, H. Jain, G. Gupta,
41 [28] R. V. Karl-Heinz Gonschorek, Electromagnetic Compatibility for S. B. Arya, Mater. Des. 2014, 63, 89–99.
42 Device Design and System Integration, Springer, 2009. [54] Z. Xu, H. Hao, J. Alloys Compd. 2014, 617, 207–213.
43 [29] M. H. Al-Saleh, U. Sundararaj, Carbon N. Y. 2009, 47, 1738– [55] Y. Yang, M. C. Gupta, K. L. Dudley, R. W. Lawrence, Adv.
44
1746. Mater. 2005, 17, 1999–2003.
[30] M. Terrones, O. Martı́n, M. González, J. Pozuelo, B. Serrano, [56] Z. Chen, C. Xu, C. Ma, W. Ren, H. M. Cheng, Adv. Mater.
45
J. C. Cabanelas, S. M. Vega-Dı́az, J. Baselga, Adv. Mater. 2013, 25, 1296–1300.
46
2011, 23, 5302–5310. [57] M. Crespo, M. González, A. L. Elı́as, L. Pulickal Rajukumar, J.
47
[31] M. H. Al-Saleh, W. H. Saadeh, U. Sundararaj, Carbon N. Y. Baselga, M. Terrones, J. Pozuelo, Phys. Status Solidi – Rapid
48 2013, 60, 146–156. Res. Lett. 2014, 8, 698–704.
49 [32] R. Jan, A. Habib, M. A. Akram, I. Ahmad, A. Shah, M. Sadiq, [58] M. González, M. Crespo, J. Baselga, J. Pozuelo, Nanoscale
50 A. Hussain, Mater. Res. Express 2017, 4, 35605. 2016, 8, 10724–10730.
51 [33] N. Yousefi, X. Sun, X. Lin, X. Shen, J. Jia, B. Zhang, B. Tang, [59] M. González, J. Baselga, J. Pozuelo, J. Mater. Chem. C 2016,
52 M. Chan, J. K. Kim, Adv. Mater. 2014, 26, 5480–5487. 4, 8575–8582.

Chem. Rec. 2018, 18, 1 – 11 © 2018 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim Wiley Online Library 9
 Pe r s o n a l A c c o u n t THE CHEMICAL RECORD

1 [60] Y. Li, J. Chen, L. Huang, C. Li, J.-D. Hong, G. Shi, Adv. [73] S. P. Pawar, D. a. Marathe, K. Pattabhi, S. Bose, J. Mater.
2 Mater. 2014, 26, 4789–93. Chem. A 2015, 3, 656–669.
3 [61] D. X. Yan, H. Pang, B. Li, R. Vajtai, L. Xu, P. G. Ren, J. H. [74] K. Singh, A. Ohlan, V. H. Pham, B. R. S. Varshney, J. Jang,
4 Wang, Z. M. Li, Adv. Funct. Mater. 2015, 25, 559–566. S. H. Hur, W. M. Choi, M. Kumar, S. K. Dhawan, et al.,
[62] D.-X. Yan, H. Pang, L. Xu, Y. Bao, P.-G. Ren, J. Lei, Z.-M. Li, Nanoscale 2013, 5, 2411–20.
5
Nanotechnology 2014, 25, 145705. [75] A. P. Singh, M. Mishra, P. Sambyal, B. K. Gupta, B. P. Singh,
6
[63] B. P. Singh, D. K. Saket, A. P. Singh, S. Pati, T. K. Gupta, A. Chandra, S. K. Dhawan, J. Mater. Chem. A 2014, 2, 3581–
7 V. N. Singh, S. R. Dhakate, S. K. Dhawan, R. K. Kotnala, 3593.
8 R. B. Mathur, J. Mater. Chem. A 2015, 3, 13203–13209. [76] M. Mishra, A. P. Singh, B. P. Singh, V. N. Singh, S. K.
9 [64] X. F. Zhang, X. L. Dong, H. Huang, Y. Y. Liu, W. N. Wang, Dhawan, J. Mater. Chem. A 2014, 2, 13159–13168.
10 X. G. Zhu, B. Lv, J. P. Lei, C. G. Lee, Appl. Phys. Lett. 2006, [77] Y. Chen, Y. Wang, H.-B. Zhang, X. Li, C.-X. Gui, Z.-Z. Yu,
11 89, 1–4. Carbon N. Y. 2015, 82, 67–76.
12 [65] J. Wang, H. Zhou, J. Zhuang, Q. Liu, Phys. Chem. Chem. [78] B. Shen, W. Zhai, M. Tao, J. Ling, W. Zheng, ACS Appl.
13 Phys. 2015, 17, 3802–12. Mater. Interfaces 2013, 5, 11383–11391.
14 [66] P. Saini, V. Choudhary, N. Vijayan, R. K. Kotnala, J. Phys. [79] Y. Chen, Y. Li, M. Yip, N. Tai, Compos. Sci. Technol. 2013, 80,
Chem. C 2012, 116, 13403–13412. 80–86.
15
[67] K. Singh, A. Ohlan, R. K. Kotnala, a. K. Bakhshi, S. K. [80] A. P. Singh, M. Mishra, A. Chandra, S. K. Dhawan, Nano-
16
Dhawan, Mater. Chem. Phys. 2008, 112, 651–658. technology 2011, 22, 465701.
17 [81] P. K. S. Mural, S. P. Pawar, S. Jayanthi, G. Madras, A. K. Sood,
[68] M. Crespo, M. González, J. Pozuelo, Mater. Chem. Phys. 2014,
18 144, 335–342. S. Bose, ACS Appl. Mater. Interfaces 2015, 7, 16266–16278.
19 [69] M. González, I. Martı́n-Fabiani, J. Baselga, J. Pozuelo, Mater. [82] M. Crespo, N. Mández, M. González, J. Baselga, J. Pozuelo,
20 Chem. Phys. 2012, 132, 618–624. Carbon N. Y. 2014, 74, 63–72.
21 [70] J. Yun, H. I. Kim, Polym. Bull. 2012, 68, 561–573. [83] M. Bayat, H. Yang, F. K. Ko, D. Michelson, A. Mei, Polym.
22 [71] M. S. Cao, J. Yang, W. L. Song, D. Q. Zhang, B. Wen, H. B. (United Kingdom) 2014, 55, 936–943.
23 Jin, Z. L. Hou, J. Yuan, ACS Appl. Mater. Interfaces 2012, 4,
24 6949–6956. Received: September 20, 2017
25 [72] R. K. Srivastava, P. Xavier, S. N. Gupta, G. P. Kar, S. Bose, Accepted: January 16, 2018
A. K. Sood, ChemistrySelect 2016, 1, 5995–6003. Published online on && &&, &&&&
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