Accepted Manuscript

Synthesis and electromagnetic characterization of frequency selective radar ab-

sorbing materials using carbon nanopowders

Davide Micheli, Antonio Vricella, Roberto Pastore, Mario Marchetti

PII: S0008-6223(14)00534-X
DOI: http://dx.doi.org/10.1016/j.carbon.2014.05.080
Reference: CARBON 9046

To appear in: Carbon

Received Date: 9 March 2014

Accepted Date: 28 May 2014

Please cite this article as: Micheli, D., Vricella, A., Pastore, R., Marchetti, M., Synthesis and electromagnetic
characterization of frequency selective radar absorbing materials using carbon nanopowders, Carbon (2014), doi:
http://dx.doi.org/10.1016/j.carbon.2014.05.080

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 1 Synthesis and electromagnetic characterization of frequency selective

2 radar absorbing materials using carbon nanopowders

1
3 Davide Micheli* , Antonio Vricella, Roberto Pastore, Mario Marchetti

4 Astronautic, Electric and Energy Engineering Department,

5 Sapienza University of Rome, Via Salaria 851, 00138 Rome, Italy

6 Abstract

7 A new method for the synthesis of multilayered radar absorbing materials is analyzed by using

8 carbon nanomaterials. With respect to the literature, a desired profile of reflection coefficient is a

9 priori established as a function of the frequency. The goal of the synthesis is to follow this target

10 profile by computing thickness and type of the material of each layer until the reflection

11 coefficient of the electromagnetic-wave absorber best approximates the wanted reflection

12 coefficient. The material available for each layer is epoxy-resin reinforced by different kind of

13 carbon-based nano/micro powders: graphene nanoplatelets, carbon nanofibers, multi-walled

14 carbon nanotubes and polyaniline. The dielectric characterization of the composite materials is

15 performed in the frequency range 2÷18 GHz. The synthesis uses evolutionary computation by

16 drawing on the electric permittivity of composite materials. Three square layered electromagnetic

17 wave absorbers of 25 cm side are manufactured. The comparison between the target, the simulated

18 and the measured reflection coefficients shows a good agreement thus confirming the scientific

19 validity of the dielectric characterization and the proposed design method. Finally, a finite element

20 analysis has been carried out to explain the mechanism of electromagnetic wave absorption by a

21 multilayer and to simulate a low radar observable naval military gun.

* Corresponding author. E-mail: davide.micheli@uniroma1.it, phone: +39/0649919758

22

23 1 Introduction

24 The research activity on electromagnetic-wave absorbers started during the second world war by

25 Germans in response to the success the Allies were having with the early radar sets [1]. Germans

26 developed a ferrite-based radar absorbing paint which was the first radar absorbing material

27 (RAM) artificially conceived. After that, there was a rapid evolution of the research and above all

28 stealth fighters were developed. The larger the aircraft the higher the possibility to be detected at

29 greater distances, thus negating much of the aircraft speed advantage. So, as bombers grew to the

30 size of the B-52, and with the “cold war” and spy planes 1950s, it became imperative to minimize

31 the enemy radar effectiveness. Even though stealth technology minimizes other “observables” as

32 well, including any kind of energy emissions that might be observed by an opponent, the most of

33 stealth technologies are directed to reduce the radar cross section (RCS) [2] by an appropriate

34 shaping and by using radar absorbing structures and materials. Nowadays, RAMs are also applied

35 in a large variety of fields such as aerospace and aeronautics, electromagnetic (EM) protection

36 from natural phenomena (lightning) and intentional interference [3,4], high-intensity radiated

37 fields (HIRF) protection [5], nuclear physics, shields adopted in particle accelerators [6], nuclear

38 EM pulses (NEMP) protection [7], electromagnetic compatibility (EMC), equipment-level

39 shielding [8-9], anechoic chambers for the realizations of wedges and pyramidal arrays [10], and

40 human exposure mitigation [11]. This research is focused on the study of RAMs in the frequency

41 range 2÷18 GHz by using layered composite materials reinforced with carbon nanomaterials. In

42 the literature a variety of studies on RAMs made by using nanomaterials is available [12-34].

43 Some studies deal in the absolute minimization of reflection coefficient (RC) within a large

44 frequency band by iterative code programs [35-47]. Anyway, by addressing the absolute

45 minimization of RC in a large frequency band, the drawback is that it is not easy to decide or
46 predict in advance at which frequencies the lowest values of RC will drop [42,47]. With respect to

47 the literature, the present research develops a new method of RAM design which allows to

48 optimize the reflection properties by following a desired profile of the RC a priori established. The

49 main advantage is to optimize the EM absorption exactly where is needed within a certain

50 frequency band. As an example, this approach could be useful to design an absorber for the human

51 exposure mitigation limited to the frequency band around 2 GHz, which is currently exploited for

52 microwave oven, mobile telecommunications, Wi-Fi, or to maximize the absorption in the X-band

53 (8.2-12.4 GHz) to reduce the radar footprint. Other applications include the development of

54 antenna radomes which could be required to be quasi-transparent in some frequencies used for

55 telecommunications and simultaneously should be able to absorb radar frequencies in different

56 bands. Curve fitting is the process of constructing a curve, or mathematical function, that best fits

57 a series of data points, possibly under certain constraints. Such approach, on the other hand,

58 doesn’t allow large room for the RAM thickness minimization, this last being mainly affected by

59 the dielectric characteristics of the available materials. The layered RAM optimization criteria here

60 adopted are deeply discussed and also experimentally validated by comparing the theoretical

61 simulations to the target RC as well as to the measurements of the RC of three manufactured

62 square layered RAM tiles. In section 2 the nano-materials description, the nano-composite samples

63 manufacturing and their dielectric characterization are analyzed. In section 3 the mathematical

64 model of the layered absorber and the objective functions minimized by the optimization

65 algorithm are presented. In section 4 the results of the simulation of several layered RAM tiles,

66 their manufacturing, and the comparison between target, simulated and finally measured RC are

67 fully described. The obtained results are then discussed in section 5. This sequence of steps is

68 needed in order to make the design evolve from a typical minimization framework toward a more

69 sophisticated and reliable mimic capability: thus, the claimed concept of “synthesis” is referred to
70 a procedure able to obtain a response of some parameters as closer as possible to a prefixed

71 specific target (in this case the material microwave RC). In section 5 a numerical analysis of the

72 EM absorption behavior at different frequencies is also provided by applying the finite element

73 method (FEM) technique. Finally, in section 6 the FEM simulation of a RAM applied to reduce

74 the radar signature of a simplified geometry naval military gun is analyzed.

75 2 Materials

76 2.1 Nano-sized materials description and morphological analysis

77 In the following sections the nanofiller description is provided. The composite matrix employed is

78 the bi-component epoxy resin PrimeTM 20LV (density 1.123 g/cm3) with own specific hardner

79 (density 0.936 g/cm3), purchased at Gurit. It has a very low mixed viscosity, long working time,

80 and an exceptionally low exothermic characteristic, which allows thick sections to be

81 manufactured without risk of premature gelation due to exothermic temperature rises. Composite

82 materials reinforced by multi wall carbon nanotubes (MWCNT) are studied for their interesting

83 microwave absorption capability, as widely known from the literature [8,21,33,35,45]. Industrial

84 grade MWCNT were employed: they are the Nanocyl™ NC 7000 (average diameter around 9.5

85 nm, average length 1.5µm, carbon purity 90%, metal oxide 10%, surface area 250-300m2/g)

86 supplied by Nanocyl. As reported in the NC 7000 technical datasheet, the volume resistivity

87 (ohm·cm) and the surface resistivity (ohm·sq) of NC 7000 MWCNT decrease from 1015 and 1013

88 to 103 and 102 respectively when the weight percentage increases from 0% to 3%. In addition,

89 three more typologies of carbon-based micro/nanoparticles, namely the carbon nanofibers (CNF),

90 the graphite nanoplatelets (GNP) and the polyaniline (PANI), have been investigated in terms of

91 their capability to affect the EM properties of the polymeric matrix. CNF were purchased at Sigma

92 Aldrich: they are cylindrical nanostructures with graphene layers arranged as stacked cones, cups

93 or plates. These very thin fibers have been attracted the attention of the researchers by virtue of
 94 their impressive mechanical, electrical and thermal properties. In particular, Endo et al [48]

95 reported the intrinsic resistivity of highly graphitic vapor-grown carbon nanofiber at room

96 temperature to be 5×10-5 Ω·cm, which is near the resistivity of graphite. Due to their high

97 electrical conductivity and high aspect ratio, CNF can impart equivalent electrical conductivity to

98 a composite at lower loadings than conventional conductive fillers do. GNP were provided by XG

99 Sciences (xGNP C-750): they are unique nanoparticles consisting of short stacks of graphene

100 sheets having a platelet shape, now becoming increasingly available. The GNP are very thin flat

101 particles (1-20 nm in thickness) with large diameters (1-50 μm). PANI emeraldine base powder

102 with conductivity value of 4-6 S/m and 2-3 μm of particle size were purchased at Sigma Aldrich.

103 PANI is a conducting polymer of the semi-flexible rod polymer family. Amongst the family of

104 conducting polymers and organic semiconductors, polyaniline has many attractive processing

105 properties, and, because of its rich chemistry, is one of the most studied conducting polymers of

106 the past 50 years [49]. Some scanning electron microscope (SEM) micrographs of the materials

107 employed are reported in Figure 1 while in Table 1 their morphological properties are

108 summarized.

109

110

111

112

113

114 Table 1. Main physical characteristics of the carbon-based powder employed.

 Carbon Specific Aspect
Material Dimension Surface Area Ratio
(wt%) (m2/g) (L/D)
MWCNT av. diameter 9.5 nm 250 ÷ 300 ~ 150
(0.5 ÷ 2.0) av. length 1.5 µm
CNF inner diameter ~ 60 10 ÷ 100
(0.5 ÷ 3.0) 0.5-10nm
outer diameter
80-200nm
length 0.5-20µm
GNP diameter 1-50µm 750 -
(0.5 ÷ 3.0) platelet thickness 1-20nm
PANI particle size 2-3µm - -
(0.5 ÷ 2.5)
115

116
117

118 Figure 1. SEM micrographs of the carbon nanoparticles employed: a) MWCNT, b) CNF, c) GNP.
119 2.2 Composite samples manufacturing and dielectric characterization

120 The proposed RAMs are based on a multilayered material where each layer is made of epoxy-

121 based composite material reinforced by different weight percentages of micro/nano-powders. The

122 first step was the manufacturing of composite material samples in order to compute the relative

123 permittivity as function of the frequency of the applied EM field. Retrieval of the dielectric

124 parameters was obtained by measuring the microwave scattering parameters Sij (S11,S21,S12,S22) by

125 means of a vector network analyzer (AGILENT, PNA-L N5235) and a coaxial transmission line

126 [50-53]. The nanofillers have been dispersed within the epoxy resin at different weight

127 percentages with step of 0.5%, in particular: MWCNT from 0.5 to 2.0wt%, CNF from 0.5 to

128 3wt%, GNP from 0.5 to 3wt%, and PANI from 0.5 to 2.5wt%. Each filler-wt% combination

129 represents an element of the database of available materials: the synthesis algorithm will access to

130 this database to select the more appropriate material for each layer of the final RAM. The

131 maximum amount of MWCNT filler has been appositely limited to 2.0wt%, due to the difficulty to

132 disperse such kind of nanoparticles within the epoxy matrix. Higher weight percentage of

133 MWCNT could be used, but practically this would limit the scalability and would increase the

134 costs of the industrial production. As far as the authors experience is concerned, such filler

135 percentages represent a trade-off between the advantages in terms of EM absorption capability and

136 the disadvantages due to the practical difficulties in achieving homogeneous dispersions with

137 higher concentrations. The critical point is achieving a nanoparticles dispersion [54] in the resin

138 with homogeneous and isotropic distribution, which is hindered by the van der Walls forces that

139 tend to aggregate the nanoparticles to each other. During the materials preparation, the dispersion

140 of the carbon powders within the polymer matrix has been achieved by sonication at room

141 temperature. The sonication was carried out at 20 kHz for about 4 hours by means of Sonics

142 Ultrasonicator (VCX750 model), setting 20% amplitude with respect to the full-scale oscillation
143 magnitude of the ultrasonic processor. The polymerization takes about 16 h around 50 °C. In

144 Figure 2 a SEM micrograph of the composite filled with MWCNT at 2wt% is reported in order to

145 put in evidence the disentanglement and the dispersion of the nanotubes after the mixing treatment

146 (with respect to the hard-packed MWCNT morphology visible in Figure 1a), as well as the

147 composite final homogeneity. Four cylindrical samples of the same kind of nano-reinforced

148 composite material were manufactured and measured for each weight percentage to be aware of

149 the reproducibility of the dielectric characterization results. The average value of real and

150 imaginary part of permittivity was taken into account. The samples electrical permittivity from

151 transmission line measurements has been retrieved by processing raw data with numerical

152 algorithms. The Nicholson-Ross algorithms have been adopted [50,51] (all these algorithms are

153 available in the software package of Agilent measurement software - Agilent software 8571E

154 material measurement). In coaxial airline measurements on dielectric slabs, small air gaps between

155 the guide walls and the dielectric sample are found to be capable of radically altering the complex

156 reflection and transmission coefficients of the excitation mode [55]. In order to minimize the

157 leakage of microwaves in the air-gaps, the samples have been lightly machined over tolerance

158 taking care to force them in the coaxial air-line, thus allowing to minimize the uncertainties.

159

160

161

162

163

164

165
166

167 Figure 2. SEM image of the fracture surface of a MWCNT 2wt% filled composite sample.

168

169 2.3 Analysis of the permittivity measurements

170 In Figure 3 the average values of real and imaginary part of electric permittivity of realized

171 materials are plotted. Several considerations can be outlined by the analysis and the comparison of

172 the obtained results. The composites reinforced by wire-shaped nanoparticles, i.e., CNT and CNF,

173 show the most effective performances in terms of EM power absorption capability. In particular,

174 CNT-filled materials highlight impressive increases of both real and imaginary part of the

175 dielectric permittivity (see Figure 3a,b) with respect to the naked resin (red curves), even at the

176 lowest concentration (0.5wt%). Also the dependence of the permittivity on the inclusion weight

177 percentage turns out well defined for these materials, as clear from the quite regular spacing

178 between the curves: the greater is the CNT/CNF inclusion wt%, the higher are the corresponding

179 values of both real and imaginary permittivity over the whole microwave range analyzed (see
180 Figure 3a,b,c,d). On the contrary, GNP and PANI inclusions don’t seem to affect appreciably the

181 dielectric response of the resin at these weight percentages (see Figure 3e,f,g,h). Mainly, as far as

182 the loss mechanism (imaginary part of permittivity) is concerned, no direct influence of the filler

183 weight concentration on the composite behavior is detected, the curves being almost

184 undistinguishable. Even if further inquiries are needed to get a reliable interpretation of such

185 results, these latter seem to preliminarily point out a direct relationship between the composite

186 dielectric properties and the filler size and morphology. With specific reference to the geometrical

187 characteristics listed in Table 1, it can be noticed that CNT and CNF can be classified as 1D

188 materials (quantum wire), GNP as 2D material (quantum well), and PANI as 3D or ‘bulk’

189 material, the dimensional classification being related to the number of ‘free’ (i.e. non quantized)

190 directions for the electrons motion [56-58]. Ballistic transport properties typical of 1D systems

191 [59,60] are thus likely to play a crucial role in the observed microwave absorption effectiveness of

192 the CNT/CNF inclusions. Furthermore, wire-shaped carbon nanostructures constitute a thicker

193 conductive network within the matrix than what flat nanostructures (GNP) or microstructures

194 (PANI) can do, thus enhancing the composite capability to interact with the microwave field. In

195 other words, for the same wt% of inclusion, rod/spaghetti-like nanopowders reduce the

196 interparticle spacing more than nanoplatelets or (even more) micropowders do, thus providing for

197 a more effective (volumetric) composite filling. By following this reasoning, the aspect ratio value

198 (see Table 1) seems to be a key parameter that rules the composite-microwave interaction. Such

199 considerations are supported by the empiric observation of the much higher viscosity of the

200 CNT/CNF-reinforced mixtures when compared to the ones reinforced with the same wt% of GNP

201 and PANI. In particular, as above mentioned, the 2wt% represents a manufacturing threshold for

202 the MWCNT employed. At the same wt%, the CNF-reinforced mixtures are still suitably

203 workable, even if their behavior begins to hinder a perfect homogeneous mixing. On the contrary,
204 in this range of concentrations the GNP/PANI addition doesn’t affect the matrix thinness

205 appreciably, the solutions showing up an extremely dilute fashion. Further investigations are to be

206 carried out in order to assess if a sharp increase of the GNP/PANI concentration (i.e. till 10÷20

207 wt%) can be useful to achieve better results in terms of microwave absorption capability.

208

209
210

211 Figure 3. Real and imaginary part of a,b) CNT, c,d) CNF, e,f) GNP, and g,h) PANI-filled

212 composites relative permittivity.

213 3 Mathematical model and objective functions

214 One original novelty of this research is the objective function (OF) minimized by means of the

215 optimization algorithm in order to follow the RC desired profile. Only some basic reminder are

216 reported to facilitate the understanding of the OF used for the synthesis of the EM absorber.

217 Details of mathematical model of the EM absorber and a description of the optimization

218 algorithms can be found in the literature [61,62]. The model consists in a multilayered structure as

219 shown in Figure 4, where each layer is made of one of the nanocomposite material (identified by

220 the filler type and its wt% of inclusion within the matrix) among those available in the database

221 obtained by means of the preliminary dielectric characterization.

Incident EM Reflected EM

Field Eu++1 E −
u +1 field

u+1 Ziu εu+1 μu+1 ηiu+1=Z0

u Ziu-1 tu εu μu ηiu

u-1 tu-1 εu-1 μu-1 ηiu-1

Zi1

1 t1 ε1 μ1 ηi1

0 PEC

x
222

223 Figure 4. General multilayer scheme of layered EM absorber. The back layer is a perfect electric

224 conductor (PEC).

225 Each layer (u) is denoted by its proper thickness tu and complex permittivity εu (that is function of

226 the frequency f ). The layers are progressively numbered from the lower side, where the material is

227 supposed interfaced with a perfect electric conductor (PEC), up to the top face where the first layer

228 is interfaced with free space (air). The electric field component of the incident EM wave is called

229 E+, the reflected part is E–. By following the scheme of Figure 4, the RC at the air-absorber

230 interface can be evaluated by the (1), which relates the free-space impedance to the input

231 impedance seen at the air-multilayer structure interface,

Z iu − Z 0
232 RCi = , (1)
Z iu + Z 0

233 where Z 0 = μ 0 / ε 0 ≅ 377 Ω is the free-space impedance, and Ziu is the input impedance at the air-

234 absorber interface at the i-th value of frequency. The input impedance of the multilayer, which is

235 seen at the air-absorber interface, can be expressed by iterating the following relationship

Z iu −1 cos(k iu t u ) + jη iu sin (k iu t u )
236 Z iu = η iu (2)
η iu cos(k iu t u ) + jZ iu −1 sin (k iu t u )

237 for each layer. In (2) tu = xu-1 – xu, is the thickness of the u-th layer and ηiu the EM intrinsic wave

238 impedance of layer u at the i-th value of frequency f

μ0 μ ru
239 ηiu = (3)
ε0 ε ru

240 where ε0 and μ0 are the electric permittivity and magnetic permeability of vacuum, while εr and μr

241 are the relative electric permittivity and magnetic permeability obtained by the measurements of

242 basic materials (see section 2.3). From the measurements carried out on the dielectric parameters it

243 has been observed that the relative permeability µ r is 1 for all the materials under test. In (2) the

244 complex wave number kiu is

245 k iu = 2π f i μ 0ε 0 (ε ru′ − jε ru′′ ) (4)

246 where fi is the i-th frequency value of the incident EM wave, and ε ru′ (ε ru′′ ) is the real (imaginary)

247 part of the u-th layer relative permittivity. In these multilayer structures, the thickness of each

248 layer can range from 0 to 16 mm, while the number of layers is upper-bounded to maximum 10

249 layers. The effective number and the thickness of the layers is established by the optimization

250 algorithm, called winning particle optimization (WPO), which is able to remove one or more

251 useless layers from the multilayered material. The order of the materials is not a priori fixed: the

252 WPO algorithm chooses which material of the database has to be used for each layer. Other

253 algorithms, like genetic algorithms (GA) or participle swarm optimization (PSO) [47,62] can be

254 used as well. The minimization procedure tries to find the best solution until the RC has “imitated”

255 an input RC target preliminarily defined and called target reflection coefficient (RCT). The WPO

256 algorithm works with a set of N particles literally jumping within the space of solutions in search

257 of the lowest value of the objective function. Calling fi the i-th frequency value within the

258 frequency band, p one particle representing the thickness and the materials of a layered RAM,

259 RC ip the value of the reflection coefficient of the current layered RAM represented by p particle,

260 and RCTi the target, i.e., the desired value of reflection coefficient at the i-th value of frequency,

261 then the OF to be minimized is

(RCT
ì = f _ stop
− RCip )
2

+ (1 − α )T p
262 OF = α
p
∑ (RCT
ì = f _ start
i

+ RCi )
p 2
. (5)
i

p
263 In (5) RC i and RCTi are expressed in linear scale, T p is the thickness of the p-th layered RAM,

264 i.e., the sum of thickness of all layers, and αis a weight parameter in the closed range 0÷1. This

265 latter allows to set if the optimization procedure has to privilege the imitation of the target (defined

266 by the first term of the right member in (5)) or the minimization of the overall thickness. For each

267 searching particle p the WPO algorithm computes the corresponding OF p , and finally the
268 configuration of the layered RAM having the lowest value of OF p is selected. Details about the

269 WPO search algorithm can be found in works already published by the authors [63,65].

270 4 Results

271 Seven different RCT profiles called RCT1- RCT7 have been proposed and addressed: they’re

272 indicated by the red lines in the plots of Figures 7-13. The output of the layer sequence of the

273 simulated and manufactured absorbers are reported in Table 2, whereas the output of the only

274 simulated layered absorbers are reported in Table 3. The αparameter is also reported in the tables:

275 sometimes different values of αhave been fixed to search different solutions for the same RCT

276 profile, the corresponding RAM simulations are denoted by s1, s2, s3. By following the different

277 RCT simulations of Table 2, three layered square RAM tiles have been manufactured. In order to

278 experimentally validate the modeling and the measurements of the electric permittivity of the

279 materials in the database, their RC measurements have been compared to the simulations (and to

280 the corresponding RCT). The manufactured RAM tiles are 25 cm side: the (relatively) large

281 dimensions allowed to adopt the naval research laboratory (NRL) arch system [66,67] to perform a

282 reliable measurement of the multilayered materials RC. About the tiles realization, the powder-

283 reinforced mixtures have been worked as described in section 2.2, the process ending with the

284 casting within a square mold and with the subsequent distribution of the mixture in order to

285 control the final thickness of each single layer. The manufacturing operations have been manually

286 performed layer by layer in order to obtain the final implemented multilayered artifact. Each layer

287 of the multilayer tile is built one over the other, and accurately defined in thickness by means of an

288 in-house assembled screw controlled press (see Figure 5a). Starting from the material designed for

289 an external layer, the composite liquid mixture is poured in excess within the mold and its level

290 adjusted by the press (some holes on the press upper plate allow the material surplus to flow out);
291 a precision of 0.1mm in the final layer thickness can be achieved by controlling the press screw’s

292 thread. Following the designed sequence, the layers are added one after the one to the previous:

293 each curing step requires about 16 hours (at 50°C) to make a layer reach complete polymerization,

294 the current process of multilayer manufacturing may thus require several days (depending on the

295 layers number) to be successfully completed.

296

297

298 Figure 5. Pictures of the multilayered tiles manufacturing: a) screw based mold system for the

299 layering control, b) final multilayered tile specimen.

300

301 The EM reflectivity of the layered absorbing composites has been measured using the vector

302 network analyzer connected to two antennas at approximately 0° incidence angle by means of the

303 NRL arch system shown in Figure 6. This latter is an industry standard for the measuring of the

304 reflectivity of materials, originally designed for testing devices at oblique incidence and over a

305 wide frequency range. Reflectivity is defined as the reduction in reflected power caused by the
306 introduction of the absorbent material. Such power reduction is compared to a ‘perfect’ reflection

307 which is very well approximated by the reflection of a flat metallic plate. The perfect reflection

308 around the 0 dB level of reflectivity is the reference level taken for the calibration of the NRL

309 Arch. The simulated RAM related to the first target RCT1 has a total thickness of 2 mm. It consists

310 of two layers of composite-reinforced by MWCNT at 1wt% and 0.5wt%. A PEC is simply added

311 to the RAM scheme in order to show that RAMs backed by a PEC are considered in the

312 simulation. In Figure 7 the measurement results are compared to the simulations as well as to the

313 target curve (RCT1) a priori established (the NRL Arch calibration reference level is also shown).

314 By this way, two other targets (RCT2 and RCT3) have been proposed, the relative optimization

315 carried out, and the RC of the manufactured tiles measured: in Figure 8 and Figure 9 the related

316 plots are reported. About the third case (RCT3), Figure 9 also shows the RC simulations of two

317 additional RAMs obtained by exploring different values of the α parameter in driving the WPO

318 search optimization. By decreasing αto 0.4 (RCT3s2) and 0.3 (RCT3s3), the algorithm tried to

319 reduce the RAM total thickness and to simultaneously follow the RC target by adding more

320 thinner layers and sophisticating the layered structure as in RCT3s2 or just reducing the structure

321 to a two layered RAM as in RCT3s3. Target RCT4 is quite complex than RCT3 since there are

322 more squared shape points of the target profile and the flat part at -20 dB is extended in frequency

323 (see Figure 10). As far as the RCT5 is concerned, it moves down to -30 dB in the frequency band

324 8-13 GHz (see Figure 11). This RCT5 profile represents the highest absorption of the EM field and

325 is quite hard to be imitated saving the RAM thickness. In RCT5 the comparison between two

326 simulations based only on CNT-composites with different α (0.4 and 0.9) and a third simulation

327 with all the available materials and α= 0.4 is shown. As far as the RCT6 is concerned, it moves

328 down to -20 dB in the frequency band 3-13 GHz (see Figure 12). This RCT profile represents a
329 difficult task to be addressed due to the large frequency band of EM field absorption. For RCT6

330 the comparison between two simulations based only on CNT at different α (0.5 and 0.6) is

331 reported. In RCT7, the target RC of -10 dB is fully extended from about 2.5 to 15.5 GHz: two

332 simulations made by accessing to the whole database are shown for α= 0.9 and α= 1.0 (see Figure

333 13).

334

335

336

337

338

339

340

341

342

343

344

345

346

347

348 Table 2. Details of design and composition (materials and layer thickness) of different

349 electromagnetic wave absorbers simulated, manufactured and measured: RC Target is the final

350 profile to imitate (red curve in the corresponding figures), αis the weight parameter used in the

351 simulation.
 RC Target α Materials Thickness Total
and layers of layers Thickness
(mm) (mm)
RCT1 MWCNT 1.0wt% 0.7 ≅2.0
Only CNT 0.6 MWCNT 0.5wt% 1.3
(Figure 7) (PEC)
RCT2 Resin 1.9 ≅9.4
Only CNT MWCNT 1.0wt% 1.5
(Figure 8) 0.6 MWCNT 1.5wt% 6.0
(PEC)
RCT3s1 Resin 4.1 ≅16.5
Only CNT MWCNT 1.0wt% 3.6
(Figure 9) 0.6 Resin 8.0
MWCNT 1.5wt% 0.8
(PEC)
352
353
354
355
356
357
358
359
360
361

362 Table 3. Details of design and composition (materials and layer thickness) of different

363 electromagnetic wave absorbers simulated: RC Target is the final profile to imitate (red curve in

364 the corresponding figures), αis the weight parameter used in the simulation.
 RC Target α Materials Thickness Total
and layers of layers Thickness
(mm) (mm)
RCT3s2 PANI 2.0wt% 3.7 ≅11.3
All Materials, MWCNT 1.5wt% 3.0
only GNP C750 3.0wt% 0.5
Simulation 0.4 MWCNT 2.0wt% 0.1
(Figure 9) CNF 3.0wt% 3.2
CNF 2.0wt% 0.1
CNF 2.5wt% 0.7
(PEC)
RCT3s3 MWCNT 2.0wt% 0.5 ≅2.7
Only CNT, 0.3 Resin 2.2
only (PEC)
Simulation
(Figure 9)
RCT4s1 Resin 3.56 ≅14.27
Only CNT, MWCNT 0.5wt% 2.07
only 0.4 MWCNT 1.0wt% 0.79
Simulation MWCNT 1.5wt% 7.83
(Figure 10) (PEC)
RCT4s2 GNP 750 0.5wt% 1.53 ≅12.43
Only CNT, PANI 1.5wt% 2.08
only 0.4 MWCNT 1.0wt% 0.89
Simulation CNF 1.0wt% 0.80
(Figure 10) MWCNT 2.0wt% 7.11
RCT5s1 Resin 3.30 ≅10.28
Only CNT, MWCNT 0.5wt% 0.75
only 0.4 MWCNT 1.0wt% 6.23
Simulation (PEC)
(Figure 11)
RCT5s2 GNP 750 0.5wt% 2.65 ≅12.61
All Materials, PANI 2.0wt% 1.11
only 0.4 MWCNT 2.0wt% 0.19
Simulation CNF 3.0wt% 1.43
(Figure 11) MWCNT 2.0wt% 7.20
(PEC)
RCT5s3 Resin 3.66 ≅20.32
All Materials, MWCNT 0.5wt% 3.56
only 0.9 MWCNT 1.5wt% 8.00
Simulation MWCNT 1.0wt% 5.10
(Figure 11) (PEC) (PEC)
RCT6s1 Resin 4.81 ≅15.7
Only CNT 0.5 MWCNT 0.5wt% 3.41
(Figure 12) MWCNT 2.0wt% 7.50
(PEC)
RCT6s2 Resin 5.08 ≅16.8
Only CNT MWCNT 0.5wt% 2.40
(Figure 12) 0.6 Resin 0.85
MWCNT 2.0wt% 8.51
(PEC)
RCT7s1 CNF 3.0wt% 5.08 ≅17.7
Only CNT CNF 3.0wt% 2.40
(Figure 13) 0.9 MWCNT 2.0wt% 0.85
CNF 3.0wt% 8.51
(PEC)
RCT7s2 CNF 1.5wt% 3.43 ≅36.6
Only CNT CNF 3.0wt% 2.33
(Figure 13) 1.0 MWCNT 1.5wt% 7.07
PANI 2.5wt% 2.49
CNT 2.0wt% 0.95
PANI 1.0wt% 4.69
CNT 1.0wt% 8.00
CNF 1.0wt% 7.64
(PEC)

365
366

367

368 Figure 6. a) NRL Arch measurement set-up (incidence angle of about 0°); b) RAM RCT3s1,

369 16.5mm, zoom view of side face.

370

371 Figure 7. Comparison between RCT1, 2.0mm RAM simulation and NRL Arch RC measurement

372 of the manufactured RAM tile (0dB calibration level is also shown).
373

374 Figure 8. Comparison between RCT2, 9.4mm RAM simulation and NRL Arch RC measurement

375 of the manufactured RAM tile (0dB calibration level is also shown).

376

377 Figure 9. Comparison between RCT3, simulation RCT3s1, with α=0.6 and thickness of 16.5mm,

378 and NRL Arch RC measurement of the manufactured RAM tile (0 dB calibration level is also

379 shown). Two more simulations, RCT3s2, 11.3mm thick, and RCT3s3, 2.7mm thick, related to

380 different WPO weight parameters, α=0.4 and α=0.3 respectively, are also plotted.
381

382 Figure 10. Comparison between RCT4s1 (only CNT) and RCT4s2 (all materials) simulations, with

383 α=0.4 and thickness of 14.27mm and 12.43mm respectively.

384

385 Figure 11. Comparison between RCT5s1 (only CNT) and RCT5s2 (all materials) simulations, with

386 α=0.4 and thickness of 10.2mm and 12.6mm respectively, and RCT5s3 (only CNT) with α=0.9 and

387 thickness of 20.3mm.

388
389

390 Figure 12. Comparison between RCT6s1 (only CNT) and RCT6s2 (only CNT) simulations, with

391 α=0.5 and thickness of 15.73mm, and α=0.6 and thickness 16.85mm respectively.

392

393

394 Figure 13. Comparison between RCT7s1 (all materials) and RCT7s2 (all materials) simulations,

395 with α=0.9 and thickness of 17.75mm, and α=1.0 and thickness 36.62mm respectively.
396

397 5 Discussion

398 5.1 Analysis of results

399 About the first two multilayered materials (related to RCT1 and RCT2 profile), the algorithm

400 shows an excellent carefulness in addressing the RC target behavior; a really good agreement

401 between the simulations and the experimental measurements is remarkable too. RCT1 and RCT2

402 profiles (Figure 7 and Figure 8) proposed to WPO have a growing number of smooth RC peaks to

403 be followed, with the aim to test the “synthesis” capability under growing constraints. In

404 particular, RCT2 intended to test the ability of the algorithm in imitating functions having a RC

405 peak at low frequency (around 4GHz), where the losses of materials are lower (thus increasing the

406 difficulty to follow the RC target). Simultaneously, in this test the WPO algorithm has been

407 required to follow other two RC peaks located around 11 GHz and 17 GHz, i.e. in the center and at

408 the end of the frequency band. The noteworthy fitting capability delivered by the “synthesis” in

409 such cases is undoubtedly assisted by the soft and smooth profile of the proposed RC targets. The

410 simulations for α = 0.6 have been highlighted since they approximate quite well the RC target

411 profile without maximizing the overall RAM thickness. The case of RCT3 profile is completely

412 different from the previous. In fact, in this case a sharp square-like behavior is proposed and the

413 deep RC peak of -20 dB is also extended over the entire X-band frequency ranging from 8.2 to

414 12.4 GHz (such RC target is currently of interest in military applications). The shape of RCT3

415 profile reported in Figure 9 doesn’t allow the synthesis to achieve the same adaptation capability

416 seen for RCT1 and RCT2 profiles. It can also be noticed that the total layered absorber thickness of

417 RCT3s1 is increased to 16.5mm, whereas it’s below 10mm in the other cases (2.0mm and 9.4mm

418 for RCT1 and RCT2 respectively). Nevertheless, the “synthesis” performed an acceptable imitation
419 of the target profile with the solution RCT3s1. As far as the RC measurement is concerned, it can

420 be noticed a reasonable agreement with the simulation RCT3s1, even if some discrepancies are

421 revealed at high frequency: the lack of a perfect fitting in frequency depends on the fully manual

422 RAM manufacturing process, which may give rise to more errors with the increasing number of

423 layers. In order to explore the algorithm full capabilities, two other solutions have been searched

424 for the same target, called RCT3s2 and RCT3s3. In these simulations the optimization parameter α

425 described in (5) has been set to α= 0.3 and α= 0.4: the aim was to check if it was possible to reduce

426 the RAM thickness while maintaining a good agreement with the RC target. Table 3 describes

427 these two additional RCT3 solutions, the related RC simulations are plotted in Figure 9. It can be

428 noticed that the ‘intermediate solution’ (α=0.4) is the most effective, since it shows a RC behavior

429 very similar to the first one, but providing a much lower tile total thickness (11.3mm vs. 16.5mm).

430 The lowest thickness constraint (α=0.3), instead, makes the WPO suggests an intriguingly thin

431 multilayer (2.7mm) but, of course, the target fitting starts to become less accurate. The two

432 additional solutions here described have not been still validated experimentally, since the tasks

433 related to very thin thicknesses and, above all, to high layers number have still to be suitably

434 tackled. In order to further investigate the ability of “synthesis” to follow even more difficult

435 target, two severe and deep profiles (RCT4 and RCT5) have been run. These profiles are rather

436 challenging since they have a lot of square contours and also a low and flat RC value of -20 dB

437 and -30 dB in the extended frequency range 8-13 GHz. For RCT4 two simulations are provided:

438 the first one is obtained by allowing the WPO to select only MWCNT-based materials, while the

439 second one is obtained by leaving to the WPO the possibility to explore the whole database

440 materials. Due to the RCT profile complexity, there is an increase of the thickness of the layered

441 EM wave absorbers with respect to the previous cases. Moreover, comparing the curves of RC
442 there’s no great advantage, except for a few better fitting, in using material other than MWCNT-

443 based (see Figure 10). That confirms the observations made in section 2.3 about the comparison of

444 MWCNT-based materials electrical permittivity with that of the other composites. For this target

445 only the simulation with α = 0.4 has been reported since for higher values of α the thickness

446 increases without any improvement in fitting the proposed profile. About the target RCT5, the

447 simulation s3 computed using α=0.9 (high thickness) has to be highlighted: as shown in Figure 11,

448 this latter approximates RCT5 profile better than s2 and s1 at low frequency, while it isn’t able to

449 adequately fit the -30 dB RC target. The RCT6 profile is not easy to be fitted due to the constraint

450 of the frequency band from 3 to 13 GHz. In particular, the optimization algorithm has been run for

451 different values of α: only the simulations carried out with α=0.5 and α=0.6 are reported as

452 examples. As expected, from the lower to the greater value of the weight parameter the total

453 thickness is increased from 15.7 mm to 16.8 mm and the ability to fit the RCT6 is increased as

454 well on the flat part of RCT curve (see Figure 12). RCT7 profile in Figure 13 was added to take

455 into account the capability of the synthesis route to find out a solution for almost the whole

456 frequency range analyzed. Comparing the solutions with those obtained in RCT6, it can be noticed

457 that relaxing the constraints in the RC level form -20 dB to -10 dB, the algorithm which

458 implements the synthesis procedure is able to imitate the RC target even for a more extended

459 frequency range. The layered materials reported in Table 2 and Table 3 are examples of

460 application of the synthesis method. The results of the synthesis of the multilayer EM wave

461 absorbers could be improved in terms of thickness reduction and absorption capability by allowing

462 the search algorithm to access to a higher number of materials in the database. In fact, the

463 capability to follow a desired RC profile depends on two main factors: one is the ability of the

464 search algorithms to explore the space of solutions escaping from local minima, the other is the
465 physical dielectric constraints due to the available materials. In particular, the materials dielectric

466 properties can strongly affect the possibility to enhance the EM wave absorption of RAMs at

467 certain frequencies. That explains why most of the RAM literature research is voted to develop

468 new types of materials able to maximize the EM wave absorption [68-75]. The main objective of

469 this research has thus been to introduce a novel way to design EM wave absorbers: this latter

470 exploits a database of different materials in order to optimize the EM absorption at the wanted

471 frequencies, thus providing a frequency selective radar absorbing material (FSRAM). Currently,

472 in the literature the primary way to obtain frequency selective EM wave absorbers are the

473 frequency selective surfaces (FSS). A FSS is any surface construction designed as a 'filter' for EM

474 plane waves. A FSS is a periodic surface whose response to incident radiation varies with

475 frequency. It can reflect, transmit, or absorb different amounts of radiation at different frequencies

476 [76-80]. The main difficulties in the FSS design is the complexity of the resonant elements

477 geometry, in particular when low and flat RC levels are required for an extended frequency band,

478 as in RAM RCT3 to RCT5 for example, and above all in the cases RCT6 and RCT7. The use of

479 carbon nanomaterials as filler in composites gives the opportunity to explore a new approach to

480 design FSS. In this approach the typical circular, squared or even more complicated geometry of

481 the resonant elements printed on the FSS layers are substituted with layers made of carbon

482 nanocomposite materials. Hence, the possibility given by the infinite combinations between the

483 different kind of carbon nanomaterials and layer thickness could enhance the possibilities to

484 design FSS. The research work here proposed is an example where the design FSRAM is

485 investigated.

486
487 5.2 FEM numerical analysis of EM wave absorption

488 In order to analyze the propagation of the EM field through the multilayer absorbers, a numerical

489 simulation based on FEM analysis was computed. In particular, the coaxial airline hosting the EM

490 absorber called RCT5s3 was simulated by using COMSOL multiphysics commercial code [81-82].

491 In Figure 14 the mesh of the coaxial airline is shown. The maximum element size of the mesh is

492 1/10 of the minimum EM wavelength (λ=3·108/fmax≅1.6 cm), while the minimum element size of

493 the mesh is of the order of 10-7 m: these dimensions enable an optimal growth of the mesh and

494 guarantee the needed accuracy in the EM analysis. In the coaxial airline, Port 1 and Port 2 are used

495 to compute the scattering parameters S11, S21. In the numerical simulation, the power set at the

496 ports is 3 dBm (2 mW) as in the real measurement. To run the FEM simulation the electrical

497 permittivity of each nanocomposite material previously measured in 2-18 GHz frequency band

498 was taken into account. In particular, the files containing the values of real and imaginary part of

499 relative electrical permittivity of each nanocomposite material were loaded as parameters within

500 COMSOL database. The EM interfaces of the code cover the modeling of EM fields and waves in

501 the frequency domain, formulating and solving the differential form of Maxwell’s equations

502 together with the initial and boundary conditions. Figure 14 represents a picture of the coaxial

503 airline and of the equivalent geometry reproduced in COMSOL.

504
505

506

507 Figure 14. a) Coaxial Air-line 7mm Agilent, b) Geometry and mesh of coaxial airline hosting four

508 layers of RCT5s3.

509

510 In Figure 15 the current density in A/m2 is shown. In particular, the red arrows represents the

511 direction and the intensity of the currents. It can be noticed that at 2 GHz the highest values of

512 current density occur in the composite materials filled by MWCNT 1.5 wt% (Figure 15a). On the

513 contrary, at 12GHz the highest values of current density occur in the second up to the half part of

514 the third layer, made respectively of composite filled by MWCNT 0.5wt% and MWCNT 1.5wt%

515 (Figure 15b). At 12 GHz the multilayer is impedance matched. In fact, the thickness and the

516 permittivity values of the second layer allow to work as a functional graded materials in which

517 layers are tailored in composition and thickness in order to enhance the EM absorption properties.
518

519 Figure 15. Current density (A/m2) within the four layers of RCT5s3 at 2GHz (a) and 12GHz (b):

520 the arrows represent the currents flow.

521

522
523

524 Figure 16. Power flow (W/m2) within the four layers of RCT5s3 at 2GHz (a) and 12GHz (b).

525

526 Expressly, by observing Figure 16 related to the power flow (W/m2) it can be understood how the

527 multilayer absorber works. At 2 GHz the RC is higher than what happens at 12 GHz, since the EM

528 wave propagates through all the layers and, due to the impedance mismatch, is reflected back to
529 the EM source at Port 1. At 2 GHz the highest power dissipation occurs mainly within the third

530 layer, made of composite filled by the highest concentration of MWCNT (see Figure 16a). On the

531 contrary, at 12 GHz the EM field is absorbed by the layered composite and the level of EM field at

532 Port 2 is lower (Figure 16b). In Figure 17 the scattering parameters S11 and S21 computed by FEM

533 are shown.

534

535 Figure 17. COMSOL FEM computation of the scattering parameters S11 and S21 of coaxial airline

536 with the four layers of RCT5s3 (only CNT).

537

538 The S11 parameters (i.e., the reflection) decreases down to -30 dB and it is in really good

539 agreement to the results shown in Figure 11 obtained with a different method of computation. As

540 far as S21 is concerned, it represents the transmission from Port 1 to Port 2 and its reduction with

541 the frequency is due to the EM absorption. S21 represents in opposite sign the EM wave shielding

542 effectiveness (SE) of layered materials and it increases with the frequency.

543
544 6 FEM simulation of simplified Naval Military Gun covered by RAM.

545 In order to study a potential application of the synthesis method we approached the FEM

546 numerical simulation of the electromagnetic field scattered by a simplified geometry of a naval

547 military gun covered with RAM RCT5s3. The objective was to reduce the gun radar foot print,

548 mainly in the front part of the gun. For this purpose, a rectangular shaped metallic structure was

549 considered as the shelter of the gun. The far electromagnetic field scattered by the front face of the

550 shelter covered with RAM has been computed and compared to that of the same structure without

551 RAM. In the computation we assumed a unitary amplitude incident plane wave of the type

552 (
Ei ( x, y ) = E + exp j 2π f μ 0 ε 0 (x cos ϕ + y sin ϕ ) ) (6)

553 where ϕdenote the incidence angle and E+ = 1 .

554 The electromagnetic numerical simulator separates incident Ei and scattered Es fields from the

555 total field Et ,

556 E t ( x , y ) = Ei ( x , y ) + E s ( x , y ) , (7)

557 so they can be plotted one at a time. We set in particular that the maximum element size of the

558 mesh cannot be greater than λ/10, where λ represents the wavelength of the plane wave of the

559 incident field. Within each RAM layer the mesh side is reduced to account for both geometric

560 complexity and wavelength reduction due to higher permittivity values. That assures a good

561 approximation in the computation of the electromagnetic field within the thinnest materials. One

562 simple way of estimating the numerical accuracy is to re-run the FEM simulations with a finer

563 mesh, for example approximately with a half-size mesh: the difference between the new and initial

564 results gives a rough estimation of the numerical error. For the calculation hereafter reported the

565 mesh was refined mainly in the regions with highest values of EM field gradient. Concerning the

566 accuracy evaluation, a systematic assessment of the FEM analysis has been performed in previous
567 works (see for example Ref. [39], where a validation of the numerical simulations with

568 experiments is discussed, finding a very good agreement within the microwave range of interest).

569 In Figure 18 the side dimensions of the simplified gun system has been assumed of 1m×2m for the

570 rectangular metallic shelter and 1m×0.2m for the metallic gun.

571

572

573 Figure 18. Simplified naval military gun geometry having the front face covered by RAM

574 (RCT5s3).

575

576 The RAM is applied on the front surface of the rectangular shelter whereas the gun is assumed

577 exposed to radar detection. The cylindrical perfectly matched layer has the function of a perfect

578 EM wave absorber which delimits the domain of computation. When appropriately tuned, this

579 layer absorbs all outgoing wave energy in frequency-domain problems, without any impedance

580 mismatch (causing spurious reflections) at the boundary. The condition of far field is assumed in
581 the FEM numerical simulation. Figure 19 reports the total and the scattered electric field by the

582 naked gun system compared to the results obtained when the front face is covered by RAM. A 0°

583 incidence angle is assumed for the EM propagation in the direction of the surface covered by

584 RAM. In Figure 19a,b the total electric field as in (7) is shown. It can be noticed that the gun

585 system produces a shadow on the opposite (left) side. As far as the reflection coefficient is

586 concerned, the naked metallic gun system produces a strong EM reflection toward the direction of

587 the EM radar source.

588
589 Figure 19. Electric field in V/m at 12GHz: a) total electric field on the naked metallic gun system;

590 b) scattered field around naked metallic gun system; c) total field around RAM RCT5s3–covered

591 gun system; d) scattered field around RAM RCT5s3–covered gun system.

592

593

594 On the contrary, the gun system where RAM is applied does not seem to reflect any appreciable

595 EM field thus reducing the scattered electric field as quite well visible in Figure 19c,d. In Figure

596 20a and 20b a zoom of the scattered electric field (V/m) and of the power loss density (W/m3)

597 within the four layers of RAM RCT5s3 are respectively shown.
598

599 Figure 20. Zoom of FEM simulation: a) the scattered electric field in V/m, b) the power loss

600 density in W/m3 within the four layers of RAM RCT5s3 at 12GHz, for the same adopted excitation

601 conditions. As expected, the higher absorption occurs in the layers filled by MWCNT 0.5-1.5wt%

602 where EM propagates with highest losses do the impedance matching condition.

603

604
605 It can be observed that the higher intensity of power loss density (W/m3) takes place in the second

606 up to the half part of the third layer of the RAM, made respectively with MWCNT at 0.5wt% and

607 MWCNT at 1.5wt%. Such feature is due to the impedance matching condition which at 12GHz

608 allows for the highest EM wave absorption. In Figure 21 the RCSs in dB of the naked and RAM-

609 covered gun system are shown. RCS is a measure of how much radar detectable an object is: a

610 larger RCS indicates that an object is more easily detected. Several factors determine how much

611 electromagnetic energy returns to the source: target material, absolute and relative target size (in

612 relation to the wavelength of the illuminating radar), incident angle (the angle at which the radar

613 beam hits a particular portion of target, depending on the target shape and orientation to the radar

614 source), reflected angle (the angle at which the reflected beam leaves the hit part of the target, it

615 depends on the incident angle), polarization of transmitted and received radiation with respect to

616 the target orientation. The RCS is strictly connected to the target reflectivity : its formal definition

617 can be found in [2]

2
Es
618 σ = lim 4πR 2 2
, (8)
R →∞
Ei

619 where Ei is the electric-field strength of the incident wave impinging on the target and Es is the

620 electric-field strength of the scattered wave at the radar. In Figure 21 it can be observed that the

621 RCS of the naked metallic gun system is well greater than the one of the RAM based system. The

622 single peak at 0° is due to the metallic gun which is not covered by RAM. The RCS of RAM

623 based system is quite lower up to 70° of the incidence angle: that is the most clear sign of the

624 reduction of the radar capability of target detection.

625

626 Figure 21. RCS (dB): a) naked metallic gun system; b) RAM RCT4s3 applied on the front surface.

627

628 7 Conclusion

629 This work investigated the possibility to address innovative RAM solutions by means of the low

630 cost and scaling-up carbon nanocomposite technology. With such an aim, several carbon

631 nano/micro-particles have been mixed in different weight percentages within a commercial

632 polymeric matrix. The evaluation of the dielectric permittivity was performed in the range 2÷18
633 GHz. Multi walled carbon nanotubes and carbon nanofibers have shown the better performances

634 in terms of EM absorption capability with respect to graphene nanoplatelets and polyaniline, thus

635 highlighting an intriguing influence of the filler size and shape on the composite dielectric

636 behavior. This first step provided a nanocomposite ‘microwave database’, which a numerical

637 algorithm has drawn on, in order to identify the best solutions for multilayered composites RAM

638 optimized in both thickness and EM reflectivity. The algorithm, called winning particle

639 optimization, makes the synthesis of layered radar absorbing materials by performing the

640 minimization of objective functions able to follow/imitate a desired input target of reflection

641 coefficient. Three multilayered composite tiles have been manufactured by following the

642 ‘instructions’ supplied by the algorithm solutions, and their microwave reflectivity has been

643 measured by NRL arch method and compared to the numerical simulations. The results obtained

644 so far have confirmed the goodness of the manufacturing procedure adopted, as well as the

645 reliability of the dielectric characterization of the single composite materials and, most of all, the

646 effectiveness of the developed design and optimization procedure.

647 Some simulations are related to RAM whose band of absorption is quite extended in frequency.

648 These simulations were introduced to remark the importance of the synthesis approach applied in

649 electromagnetic materials and computational analysis where a desired response can be attained by

650 combining different materials.

651 Finally, the FEM analysis has been introduced in order to easy the comprehension of concepts like

652 the EM wave absorption of a layered material due to the impedance matching condition at certain

653 frequencies.

654 A numerical FEM analysis of a simple geometry example of naval military gun covered by the

655 optimized layered RAM has been finally analyzed. In particular, it was highlighted how the RAM

656 presence reduces considerably the EM scattered field, thus paving the way to the application of
657 carbon nanocomposites for RCS reduction.

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862

863

864

865

866
867

868 Table captions

869 Table 1. Main physical characteristics of the carbon-based powder employed.

870

871 Table 2. Details of design and composition (materials and layer thickness) of different

872 electromagnetic wave absorbers simulated, manufactured and measured: RC Target is the final

873 profile to imitate (red curve in the corresponding figures), αis the weight parameter used in the

874 simulation.

875

876 Table 3. Details of design and composition (materials and layer thickness) of different

877 electromagnetic wave absorbers simulated: RC Target is the final profile to imitate (red curve in

878 the corresponding figures), αis the weight parameter used in the simulation.

879

880

881 Figure captions

882 Figure 1. SEM micrographs of the carbon nanoparticles employed: a) MWCNT, b) CNF, c) GNP.

883

884 Figure 2. SEM image of the fracture surface of a MWCNT 2wt% filled composite sample.

885

886 Figure 3. Real and imaginary part of a,b) CNT, c,d) CNF, e,f) GNP, and g,h) PANI-filled

887 composites relative permittivity.

888
889 Figure 4. General multilayer scheme of layered EM absorber. The back layer is a perfect electric

890 conductor (PEC).

891

892 Figure 5. Pictures of the multilayered tiles manufacturing: a) screw based mold system for the

893 layering control, b) final multilayered tile specimen.

894

895 Figure 6. a) NRL Arch measurement set-up (incidence angle of about 0°); b) RAM RCT3s1,

896 16.5mm, zoom view of side face.

897

898 Figure 7. Comparison between RCT1, 2.0mm RAM simulation and NRL Arch RC measurement

899 of the manufactured RAM tile (0dB calibration level is also shown).

900

901 Figure 8. Comparison between RCT2, 9.4mm RAM simulation and NRL Arch RC measurement

902 of the manufactured RAM tile (0dB calibration level is also shown).

903

904 Figure 9. Comparison between RCT3, simulation RCT3s1, with α=0.6 and thickness of 16.5mm,

905 and NRL Arch RC measurement of the manufactured RAM tile (0 dB calibration level is also

906 shown). Two more simulations, RCT3s2, 11.3mm thick, and RCT3s3, 2.7mm thick, related to

907 different WPO weight parameters, α=0.4 and α=0.3 respectively, are also plotted.

908

909 Figure 10. Comparison between RCT4s1 (only CNT) and RCT4s2 (all materials) simulations, with

910 α=0.4 and thickness of 14.27mm and 12.43mm respectively.

911
912 Figure 11. Comparison between RCT5s1 (only CNT) and RCT5s2 (all materials) simulations, with

913 α=0.4 and thickness of 10.2mm and 12.6mm respectively, and RCT5s3 (only CNT) with α=0.9 and

914 thickness of 20.3mm.

915

916 Figure 12. Comparison between RCT6s1 (only CNT) and RCT6s2 (only CNT) simulations, with

917 α=0.5 and thickness of 15.73mm, and α=0.6 and thickness 16.85mm respectively.

918

919 Figure 13. Comparison between RCT7s1 (all materials) and RCT7s2 (all materials) simulations,

920 with α=0.9 and thickness of 17.75mm, and α=1.0 and thickness 36.62mm respectively.

921

922 Figure 14. a) Coaxial Air-line 7mm Agilent, b) Geometry and mesh of coaxial airline hosting four

923 layers of RCT5s3.

924 Figure 15. Current density (A/m2) within the four layers of RCT5s3 at 2GHz (a) and 12GHz (b):

925 the arrows represent the currents flow.

926

927 Figure 16. Power flow (W/m2) within the four layers of RCT5s3 at 2GHz (a) and 12GHz (b).

928 Figure 17. COMSOL FEM computation of the scattering parameters S11 and S21 of coaxial airline

929 with the four layers of RCT5s3 (only CNT).

930

931 Figure 18. Simplified naval military gun geometry having the front face covered by RAM

932 (RCT5s3).

933
934 Figure 19. Electric field in V/m at 12GHz: a) total electric field on the naked metallic gun system;

935 b) scattered field around naked metallic gun system; c) total field around RAM RCT5s3–covered

936 gun system; d) scattered field around RAM RCT5s3–covered gun system.

937

938 Figure 20. Zoom of FEM simulation: a) the scattered electric field in V/m, b) the power loss

939 density in W/m3 within the four layers of RAM RCT5s3 at 12GHz, for the same adopted excitation

940 conditions. As expected, the higher absorption occurs in the layers filled by MWCNT 0.5-1.5wt%

941 where EM propagates with highest losses do the impedance matching condition.

942

943 Figure 21. RCS (dB): a) naked metallic gun system; b) RAM RCT4s3 applied on the front surface.

944