Vous êtes sur la page 1sur 8

Materials and Design 93 (2016) 423–430

Contents lists available at ScienceDirect

Materials and Design

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

3D printed anisotropic dielectric composite with meta-material features


D.V. Isakov a,⁎, Q. Lei a, F. Castles a, C.J. Stevens b, C.R.M. Grovenor a, P.S. Grant a
a
University of Oxford, Department of Materials, Parks Road, Oxford OX1 3PH, United Kingdom
b
University of Oxford, Department of Engineering Science, Parks Road, Oxford OX1 3PJ, United Kingdom

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

Article history: This paper presents all-dielectric materials used to 3D print coupons with spatially varying dielectric permittivity
Received 11 November 2015 and possessing high dielectric anisotropy. The coupons were directly printed through a dual-filament fused de-
Received in revised form 29 December 2015 position modelling technique utilizing bespoke feedstock filament comprised a polymer-based micro-ceramic
Accepted 31 December 2015
composite with controlled permittivity and loss. By designing the arrangement of both high and low permittivity
Available online 5 January 2016
filament materials in the printed coupons, the microwave operating frequency and magnitude of Mie-type res-
Keywords:
onances could be manipulated to provide metamaterial-like characteristics.
Additive manufacturing © 2016 Elsevier Ltd. All rights reserved.
Fusion deposition
Dielectric composites
Metamaterials

1. Introduction with graded properties and good bonding between the metal and the
ceramic phases have been produced by AM followed by sintering, incor-
Significant progress has been made in the past two decades in the porating fused silica in polypropylene [21]. Metal/polymer composites
development and commercialization of additive manufacturing (AM) combining iron particles in a nylon matrix [22] or an acrylonitrile buta-
processes such as stereolithography, selective laser sintering, solid diene styrene (ABS) matrix [23] have been developed to improve the
ground curing [1–4]. Recent generations of low-cost and office- mechanical properties of rapid tooling. Comparatively high dielectric
friendly additive manufacture printers now provide the potential to ac- permittivity alumina particulate has been loaded into a wax fugitive
cess mass-markets and to broaden additive manufacture concepts from binder for the fabrication of photonic crystal structures by AM, followed
being expensive and exclusive technologies to those that are easy-to- by burn-out of the wax [24].
use and affordable. AM processes are now used increasingly in research This rapidly growing body of work on printable materials suggests
and in small lot manufacture to build engineering components having that AM offers the possibility to control the properties of fabricated
complex geometrical shape, high material yield and reduced lead components by tailoring local composition and microstructure.
times [5–11]. AM is also used for biomedical applications such as bone This gives rise to a versatile development of AM for fabrication of meta-
scaffolds, replacement tissues, organs and biodegradable templates materials [7–10]—electromagnetic materials with engineered sub-
[12–14]. wavelength structures designed to exhibit strong coupling with the
In terms of AM using polymers as the feedstock material, thermo- electric and magnetic components of an incident electromagnetic
plastic have been investigated and applied extensively [5,7,15]. Further- wave. The focus of this paper is to consider the application of AM for
more, polymer composites containing a disperse minority fraction of the fabrication new electromagnetic materials, that after further devel-
inorganic powders materials may be processed and thus provide a opment, could be used to realize various artificial phenomena such as
broad range of thermo-physical, functional and mechanical properties. cloaking [25–27], photonic bandgap crystals [28], left-handed metama-
For example, wax-based feedstock filament with added piezoelectric terials [29,30], and novel microwave circuits and antennas [31]. The
lead zirconate titanate ceramic powder has been used to fabricate func- most common materials approach to producing artificial electromag-
tional piezoelectric devices [16,17]. Multiple feedstocks containing lead netic properties (such as negative index of refraction) required by
magnesium niobate and silver-palladium have been used as to manu- theoretical designs (such as those arising from spatial transformations
facture green components to be used as piezoelectric transducers [18], [32]) has involved metallic split ring resonators or other metal-
and paraffin-based thermoplastic feedstock with stainless steel and zir- containing sub-wavelength elements [26,33]. While many aspects of
conia powder have also used for AM of green metal-ceramic compo- theory and design can be confirmed using these types of structures,
nents [19,20]. Structured aluminium/alumina composite materials which are generally considered lossy, narrowband and present chal-
lenges for implementation in practical systems. Alternatively, high di-
⁎ Corresponding author. electric rods arranged in a much lower permittivity matrix can be
E-mail address: dmitry.isakov@materials.ox.ac.uk (D.V. Isakov). used as resonator elements [29,34], giving weaker interactions with

http://dx.doi.org/10.1016/j.matdes.2015.12.176
0264-1275/© 2016 Elsevier Ltd. All rights reserved.
424 D.V. Isakov et al. / Materials and Design 93 (2016) 423–430

applied fields but with potential for lower loss. As it will be shown The dried mixed powder-binder feedstock was milled mechanically in
below, because these structures can be readily achieved by AM, the res- a high speed grinder and resulting granules melted in a single-screw
onator approach based on dielectric arrays rather than metallic-based hot extruder to produce many metres of continuous composite filament
resonators may offer some further flexibility in practical implementa- of 1.7–1.8 mm diameter [38]. Micro-particles of different perovskite
tion, for example in geometric arrangements to produce graded index oxides such as BaTiO3 (Sigma-Aldrich), CaTiO3 (Alfa Aesar) and
materials operating at microwave frequencies. Ba0.64Sr0.36TiO3 (Trans-Tech), all with powder diameters b3μm, were
This work demonstrates the feasibility of using bespoke polymer- added to the polymer matrices, providing a range of permittivities and
based feedstock composite in AM to produce dielectric resonator struc- losses, as described later.
tures, with strong anisotropy matching the ‘Wiener bounds’ [35,36] de- The dielectric properties of as-printed materials, with no layering or
scription of property anisotropy in layered composite systems. Our anisotropic design, was carefully characterized before resonating struc-
printed structures comprise a thin coupon (d b λ, where d is the coupon tures were designed, using a split-post dielectric resonator (SPDR,
thickness and λ is the wavelength of incident microwave radiation, in QWED) technique [39] and a Rohde&Schwarz ZNB20 vector network
the range from 12 to 18 GHz) within which there alternating layers, or analyser. The resonator is designed for a nominal 15 GHz frequency
‘stripes’, of relatively low (polymer only) and high (polymer plus inor- and the actual measurements were taken at a frequency close to the
ganic particles) dielectric constant materials. These striped coupons nominal. The SPDR technique allows the determination of complex per-
can be produced in a single operation directly from a CAD file using mittivity with greater sensitivity than transmission-reflection methods,
the AM process termed fused deposition modelling (FDM). Our imple- albeit at a single frequency, and provides more reliable measurements
mentation of FDM used two continuous thermoplastic based filaments in low loss (tanδ b 0.05) materials.
as feedstock, one comprising polymer only, and the other the same Using the dielectric properties of each type of printed material, the
polymer but with a high fraction of high permittivity inorganic micro- commercial Comsol Multiphysics RF module, which is a flexible imple-
particles. The filaments were melted in the print head and then extrud- mentation of the finite element method, was used to model the wave
ed onto the forming coupon by the print head moving in the xy-plane propagation in layered or striped coupons and to suggest the relative di-
according to the CAD file. The as-manufactured coupon had high density mensions of each stripe to achieve the desired performance. A 3D model
without the need for any post-deposition processing (such as sintering, of the coupons, with predefined material properties (for each type of
machining, etching), and there was apparently good adhesion between material) observed experimentally, was constructed and the electro-
polymer and composite regions, although as with all AM structures, a magnetic field distribution together with complex scattering parame-
low fraction (b1 vol%) of internal micro-voids may persist [37]. The re- ters were computed. Guided by the model-based design, 16 ×
sponse of the coupons in different geometric orientations to incident 8 × 2 mm coupons were printed suitable for insertion following edge
microwave radiation across a range of frequencies showed, in accor- polishing into a Ku-band waveguide for characterization of dielectric
dance with effective medium theory and Weiner bounds, artificial properties using the VNA and the transmission/reflection line (TRL)
dielectric anisotropy with a birefringence Δϵ of 1.15, along with technique. The TRL technique involved measuring the two port complex
geometry-dependent Mie-type resonance effects, characteristic of scattering reflected (S11) and transmitted (S21) parameters in the fre-
metamaterial-like behaviour. quency range from 12 to 18 GHz so that the relative complex permittiv-
ity ϵr and permeability μr could then be obtained using the widely
2. Experimental employed Nicholson–Ross–Weir (NRW) extraction method [40].
The printed coupons were also characterized using a single split ring
A dual-extrusion FDM-type 3D printer (Makerbot Replicator 2) was resonator probe moving in an xy-plane above the coupon with 0.25 mm
used for the direct fabrication of rectangular coupons of polymer-based step resolution. The probe comprised a split ring (formed from a 5 mm
materials. The FMD process of building a solid object involves heating of section of 22 mm diameter copper tube of wall thickness 1 mm) fixed
the fed filament and squeezing it out layer-by-layer through a tiny between near field coupled transmitting and receiving ports connected
nozzle (0.4 mm inner diameter) onto a heated surface, via a computer to a VNA. The resulting resonant frequency of this split copper ring ar-
controlled three-axis positioning system (with a spatial resolution of rangement depends on the ring geometry and capacity of the air gap
approximately 100 μm in z-axis and 11 μm in x and y). The thermal en- in the region of the split in the ring [41]. If a material with dielectric per-
ergy imparted to the moving filament by the print head heater is partial- mittivity greater than air is placed close (b0.5 mm) to the gap in the res-
ly conducted to the previously deposited underlying layer and the onator ring, the ring resonant frequency shifts lower as a monotonic
adjacent extruded filament on contact, and provided a molecular-scale function of dielectric constant being probed and therefore the method
diffusion bonding process at the interface between the extruded fila- can be used as a spatially sensitive surface dielectric probe. The mea-
ment and pre-deposited material, resulting in good structural integrity sured permittivity from this technique differs from the bulk value and
[5]. As a result of the layer-by-layer approach, the printed objects is best-suited to indicate relative changes in permittivity only, but offers
most readily take the form of laminates, with stacked layers each con- a quick and convenient way to assess spatial variations in near-surface
taining lengths of contiguous extruded filament. properties.
To print coupons comprising relatively low and high permittivity A JEOL JSM-840 scanning electron microscope (SEM) operating at
striped regions, two types of filament (loaded onto two extruder 15 kV was used to examine the structure of the printed samples. Ther-
heads) were used simultaneously; commercially supplied acrylonitrile mogravimetric analysis of the filament feedstocks in which the polymer
butadiene styrene (ABS) or polypropylene (PP) was used for the low di- fraction was fully volatized at high temperature to measure the remain-
electric permittivity regions, while high dielectric permittivity regions ing weight fraction of inorganic particulates in the filaments was
used a mixed inorganic ceramic powder-polymer composite. The performed using a PerkinElmer PYRIS Diamond differential scanning
above mentioned polymers were chosen as the polymer matrix because calorimeter.
they are standard materials for desktop 3D printers. Additionally, the
boundary of the two printed (low-, and high-permittivity) layers must 3. Results and discussion
provide good adhesion between them. The high-permittivity filaments
were fabricated as follows. Firstly, ABS pellets and the ceramic powder 3.1. Material characterization
(various types, see later) were mixed in the target volume ratio (up to
30 vol% ceramic) and then stirred in acetone until there was total disso- Fig. 1a shows typical examples of 3D printed structures consisting of
lution of the ABS. The resulting viscous suspension was spread out uni- arrays of alternating low (ABS only) and high (ABS + micro-particles)
formly on trays in a fume cupboard and the acetone fully evaporated. permittivity stripes aligned either vertically or horizontally. The chess-
D.V. Isakov et al. / Materials and Design 93 (2016) 423–430 425

Fig. 1. a) Various printed coupons for dielectric characterization comprising stripes or other arrangements of relatively low (ABS only) and high (dielectric ceramic/ABS composite)
permittivity materials; b) and c) are experimental measurements of the spatial distribution of the resonant frequencies of the split ring probe (qualitatively representing the local
dielectric permittivity) in the 8-column (4 filled, 4 unfilled) and 4-row (2 filled, 2 unfilled) printed slabs estimated by the surface resonance probe technique.

board lattice is also shown to demonstrate the capability of the AM pro- 3D-printed high dielectric ceramic-polymer composites can be found
cess to provide a huge range of possibilities for inter-leaved low and in [38].
high permittivity materials. Fig. 1b and c show the measured spatial Fig. 2a and b show scanning electron microscope (SEM) images of the
distribution of the resonant frequencies according to the split ring boundary between a printed layer of ABS only and an ABS + 30 vol.%
probe (qualitatively related to the local, effective dielectric permittivity) Ba0.64Sr0.36TiO3 composite layer, indicating some micro-voiding in
in the 8-column (4 filled, 4 unfilled) and 4-row (2 filled, 2 unfilled) the polymer matrix. SEM micrographs show also that printed ABS +
coupons respectively. The surface probe showed good sensitivity to 30 vol.% Ba0.64Sr0.36TiO3 composite possess an acceptably dense micro-
the different printed regions and suggested that the resulting spatial structure and filler particles (b 2 μm) distributed reasonably uniformly
distribution of permittivity was qualitatively as intended. Identical cou- throughout the polymer matrix.
pons comprising only the unfilled polymer (hereafter associated with
low permittivity, ϵl) or filled polymer + ceramic particulates (high per- 3.2. Anisotropy of dielectric permittivity
mittivity, ϵh) were also printed to obtain the values for reference permit-
tivities needed in the Comsol model. An effective medium theory approach may be applied to two com-
For successful 3D printing (without blocking, extruded filament ponent composites to describe the maximum ϵmax and minimum ϵmin
breakage, merging of printed layers, etc.), the composite filament effective permittivity that might be expected from a system comprising
must have the appropriate balance of stiffness, toughness (essentially relatively low ϵl and high ϵh permittivity components, which are known
for robust handling and feeding), surface finish, small variance in diam- as ‘Wiener bounds’ (or absolute bounds) [47]:
eter, dispersion and adhesion properties, which in practice provided an
upper limit to how much inorganic particulate could be added [23]. ϵ max ¼ f ϵh þ ð1−f Þϵl ð1Þ
Table 1 shows the experimentally measured dielectric properties of var-
ious as-printed materials. The particulate volume fractions in Table 1 ϵh ϵl
ϵmin ¼ ð2Þ
were determined by thermogravimetric analysis. The maximum load- f ϵl þ ð1−f Þϵh
ing of fraction micro-particulate that could be printed reproducibly
was approximately 30 vol%. where f is the fraction of the high permittivity component. If the mixing
The measured dielectric permittivities and loss for composites with procedure arranges each of the two components in preferred, clustered
BaTiO3, Ba0.64Sr0.36TiO3 and CaTiO3 are in good agreement with data orientations then since the resulting macroscopic dielectric response is
published for polymer-ceramic composites of 0–3 connectivity dependent on the vector direction of the exciting field with respect to
[42–44]. Any slight differences might be associated with the different this arrangement, dielectric anisotropy can be achieved [36]. Noting
grades of polymers used for fabrication of the composites. Additionally, that Eqs. (1) and (2) are length-scale independent, the fraction f can
a small fraction of entrapped air/voids, that might arise as the filament is be taken as the overall fraction of the relatively high permittivity
printed [45,46] can result in reduction of the effective dielectric permit- (ABS + filler) composite material. Therefore, the overall dielectric re-
tivity. The detailed study on microwave dielectric characterization of sponse of the printed coupons in Fig. 1 (ignoring any resonance effects
for the time being and noting as previously that d b λ) should show
Table 1 dielectric anisotropy as an electric field is applied parallel or perpendic-
Printed materials and their estimated and measured dielectric permittivity and losses at ular to the orientation of the stripes, limited by the Wiener bounds.
15 GHz (ABS — acrylonitrile butadiene styrene, PP — polypropylene).
Note also that Eqs. (1) and (2) are equivalent in form to those describing
Material Particulate vol. fraction ϵr tanδ conductance and capacitance connected in parallel and in series,
ABS + BaTiO3 0.27 7.0 3.42 ×10−2 respectively.
ABS + Ba0.64Sr0.36TiO3 0.30 6.7 3.68 ×10−2 Fig. 3a shows a plot of ϵmax and ϵmin from Eqs. (1) and (2) as a func-
PP + CaTiO3 0.27 5.0 5.10 ×10−3 tion of volume fraction f of the high permittivity composite with ϵl =
ABS 2.65 4.80 ×10−3 2.65 (corresponding to printed ABS only from experiment, Table 1)
PP 2.25 2.65 ×10−4
and ϵh = 7.0 (ABS + 27 vol% BaTiO3, Table 1). Fig. 3b shows the
426 D.V. Isakov et al. / Materials and Design 93 (2016) 423–430

Fig. 2. SEM images of printed ABS + 30 vol.% filled Ba0.64Sr0.36TiO3: a) boundary between ABS and BST/ABS layers; b) distribution of the Ba0.64Sr0.36TiO3 particles throughout the ABS
polymer matrix in BST/ABS composite layer.

measured dielectric permittivity as a function of frequency for the a lower permittivity matrix [29,34,48]. Such an effect is based on Mie
printed, striped coupons with an overall fraction of high permittivity resonance (the theory of the Mie scattering can be found elsewhere
stripes of 50 vol% and with the incident electric field of the impinging [49]). Briefly, when the relative permittivity of the resonator is high
microwaves either parallel (ϵ∥) or perpendicular (ϵ⊥) to the long direc- with respect to the embedding medium, an internal subwavelength res-
tion of the stripes. The dielectric permittivity of the ABS only ϵl and onance is set up with a large displacement current (JD ∝ δE/δt, where E is
ABS + 27 vol% BaTiO3 ϵh (again from Table 1) is also shown. Initially ig- electric field, and t is time). The azimuthal component of the displace-
noring the inflexion in ϵ⊥, both ϵ∥ and ϵ⊥ were relatively stable over the ment current is greatly enhanced at the first Mie resonance resulting
frequency range at 4.8 and 3.65 respectively, and in very good agree- in a large induced magnetic field. As functions of the permittivity, mul-
ment with the predictions of Eqs. (1) and (2) shown in Fig. 3a. Overall, tiple modes can be excited within the dielectric resonator. These electric
the printed coupon showed the anisotropy of dielectric permittivity and magnetic dipole resonances act as artificial ‘atoms’ which form the
with high birefringence Δϵ = 1.15. basis of all-dielectric metamaterials. In a material made up of a collec-
Returning to Fig. 3b, the plot of ϵ⊥ showed a perturbation in the ef- tion of resonant domains, their combined scattering response can pro-
fective permittivity at 15.9 GHz. A similar effect was seen in all printed vide a material with almost arbitrary values of effective permittivity
materials with alternate low and high permittivity number of layers and permeability.
(equivalent to periods) in the case of 2, 3 and 4 high permittivity stripes Drawing on this array of dielectric rods resonator concept, the
(per coupon height). The amplitude of this perturbation became less printed alternating stripe structure presented here can now be consid-
pronounced as the width of the high permittivity stripe decreased. ered as a periodic array of rectangular-shaped dielectric resonators.
These perturbations are now described in terms of resonance effects in- Fig. 4a shows simulations of the complex transmittance and reflectance
duced by the strip-like geometry. parameters as a function of frequency for a coupon containing 4 high
permittivity stripes with ϵh = 7.0 + 0.007i, interleaved between matrix
3.3. Mie-type resonance stripes with ϵl = 2.6 + 0.003i. All simulations had the same geometric
arrangements of the propagated wave and sample as used in our exper-
Simple dielectric resonators possessing simultaneously negative ef- iments: the wave propagated normally to the coupon with the electric
fective permittivity and permeability have been reported recently for field vector oriented perpendicular to the stripes and the magnetic
the case of regular arrays of high dielectric rods or cubes dispersed in field oriented parallel to the stripes. Within the 12–20 GHz frequency

Fig. 3. a) Wiener upper (ϵmax,) and lower (ϵmin) bounds as a function of volume fraction f of the high-permittivity composite for compounds with ϵl =2.65 and ϵh =7.0, corresponding to
the ABS and BaTiO3 + ABS coupons. b) Measured real parts of the effective dielectric permittivities ϵ∥ and ϵ⊥ corresponding to the striped coupons with an overall fraction of high
permittivity stripes of 50 vol% and with the incident electric field of the impinging microwaves either parallel or perpendicular to the long direction of the stripes respectively.
D.V. Isakov et al. / Materials and Design 93 (2016) 423–430 427

Fig. 4. a) Calculated complex scattering parameters for a 4-row coupon with alternating ϵl =2.6+0.003i and ϵh =7.0+0.007i dielectric constants; b) the corresponding extracted real and
(c) imaginary parts of permittivity and permeability.

range, the simulations suggested two resonances at 15.19 GHz and These simulations showed qualitatively similar behaviour in ϵ' as seen
19.54 GHz. Using the standard NRW retrieval method [40], from the in the experiments.
simulated reflectance and transmittance data the resulting effective To understand the Mie-modes leading to resonance, the computed
real (ϵ') and imaginary (ϵ″) parts of the permittivity, and real (μ') and spatial distribution of electric and magnetic fields around the resonance
imaginary (μ″) parts of permeability as a function of frequency are frequencies were simulated using the finite element method. Fig. 5
shown in Fig. 4b (real parts) and c (imaginary parts, respectively). shows simulated distributions of electric and magnetic fields inside the

Fig. 5. a) Distribution of the electric and magnetic and fields in the slab with spatially varied dielectric permittivity near first (a, b) and second (c, d) Mie resonances. The wave was normally
incident on the slab along the z-axis with E∥x and H∥y.
428 D.V. Isakov et al. / Materials and Design 93 (2016) 423–430

Fig. 6. The experimental reflection and transmission parameters as a function of frequency obtained for two different printed polymer coupons; a) with four high permittivity stripes, and
b) with six high permittivity stripes. The solid lines are computer simulations for the coupons using ϵl =2.65+0.012i and ϵh =7.0+0.23i for the low and high permittivity striped regions
respectively.

coupon having the same dielectric properties as a real 3D printed sample experiment. These plots confirm that the resonance behaviour was
at the first (Fig. 5a and b) and second (Fig. 5c and d) resonances. The field geometry-dependent, with the resonant frequencies and dips in trans-
distributions were relatively complex due to the multiple discrete bound- mission and reflection parameters governed by the width (or period)
aries between regions of high and low permittivity. Fig. 5a shows that in of the stripes. While the resonant frequency increased slightly with
the vicinity of the first resonance at 15.19 GHz, the circular component the number of stripes, the sharp changes in S-parameters around the
of electric field (shown as concentric curves in y-plane) resulted in a com- resonant frequency were reduced.
paratively strong magnetic field (Fig. 5b). At the second resonance, the To explore resonant behaviour further, Fig. 7a and b shows simula-
strong linearly polarized displacement currents (also seen as contour tions of the transmission S21 parameter and absorption A = 1 - R - T,
curves in y-plane, Fig. 5c resulted in enhancement of the azimuthal mag- where T is the transmission coefficient and R is the reflection coefficient,
netic field (Fig. 5d). Therefore, the resonances can be associated with first behaviour of coupons with different periods (number of layers). The
TE11 mode and second TE12 mode of the Mie-resonances (magnetic and resonance effect swiftly diminished for periods N6 per coupon (i.e. re-
electric, respectively) [50,51]. ducing stripe width) probably because of the fading of the multiple scat-
According to the Mie theory, the resonant dielectric particle at the tering of the waves within the close boundaries of the neighbouring
first resonant mode is equivalent to a magnetic dipole, in which artificial dielectric rods.
polarization and resonance frequency are controlled by the particle ge- As previously described, the Mie-like resonance behaviour can also
ometry and its permittivity [29]. Consequently, the resonance frequency be tuned by changing the permittivity of the dielectric units themselves,
of the designed coupons can be governed by the size (period) of the because the frequency of the resonance modes is proportional to πc=ðω
high permittivity stripes. This was demonstrated experimentally using pffiffiffi
ϵÞ [29,51]. In order to confirm this, and recognizing that the permittiv-
two different printed polymer coupons with four and six permittivity ity of ferroelectric titanates is strongly temperature sensitive, Fig. 8
stripes. Fig. 6 shows the experimentally measured reflectance and shows the measured scattering parameters as a function of temperature
transmittance coefficients for these two coupons again with the stripes for a coupon again comprising alternate ABS + 27 vol% BaTiO3/ABS
oriented perpendicular to the electric field polarization (i.e. in the same stripes. A peak in the dielectric permittivity of BaTiO3 occurs in the vicin-
orientation as shown in Figs. 4 and 5). Fig. 6 also shows simulations of ity of the ferroelectric-paraelectric phase transition (~ 110 °C in bulk
the identical structures, in both cases showing good agreement with

Fig. 7. a) Simulations as a function of frequency for (a) the transmittance and (b) the relative absorption of the printed striped coupons, with increasing number (reducing thickness) of
stripes.
D.V. Isakov et al. / Materials and Design 93 (2016) 423–430 429

Fig. 8. Variation in transmittance with frequency of a printed coupon comprising alternating stripes of ABS and BaTiO3/ABS as a function of temperature.

BaTiO3 [52]), and Fig. 8 shows a reduction in the resonance frequency composite regions had ϵh = 5 + 0.025i (Table 1). Although less pro-
with increasing temperature from 20 °C to 105 °C. This redshift of ap- nounced than shown in the simulation because of manufacturing im-
proximately 300 MHz in S21 dip corresponded to an increase in the perfections such as retained air/voids, the relatively simple high
static dielectric permittivity of the high permittivity stripes of Δϵ = permittivity, low loss striped arrangement similarly showed strong res-
0.4. There was also a reduction in the magnitude of the S21 amplitude onance, and the onset of metamaterial-like character.
at resonance with increasing temperature that was due to the corre-
sponding strong rise in dielectric loss in BaTiO3 as the phase transi-
tion was approached. 4. Summary
While losses in the BaTiO3 containing regions increased with tem-
perature, damping out the resonant behaviour, the overall Mie-type res- The ability to fabricate new feedstock materials for 3D printing in
onance effect was governed by the dielectric loss of both the composite pursuit of practical all-dielectric artificial materials has been presented,
and polymer only regions. Fig. 9a shows a simulation of the predicted together with simulations and experimental results on preliminary
overall effective dielectric permittivity of a printed 2-period striped cou- demonstrator structures. We show that 3D printed all-dielectric struc-
pon as a function of frequency for high permittivity regions of ϵ'h = 7.0 tures offer a convenient method to move towards the manufacturing
but with different assumed low loss values. Fig. 9a shows that according of structures with metamaterial electromagnetic properties and tunable
to simulations (where permittivity is derived from the simulated reflec- operational frequencies. The designed structures consisting of oriented
tance and transmittance coefficients using the NRW method), near-zero dielectric stripes with alternating dielectric permittivity possessed
or negative permittivity i.e. metamaterial-like behaviour may be in- well-defined artificial anisotropy of effective permittivity, and a Mie-
duced if losses could be restricted to tanδ≤ 5 ×10-5. To explore this pos- type resonance. This resonance frequency could be controlled by mak-
sibility experimentally, the relatively high loss ABS polymer was ing use of the degrees of design freedom facilitated by 3D printing,
replaced by lower loss polypropylene (ϵl = 2.25 + 0.0006i, Table 1) such as the periodicity of the different units, their relative permittivities
and BaTiO3 was replaced by CaTiO3 that has a very low loss of and dielectric losses. Finally, the results show the potential for near-zero
tanδ ≈ 3 × 10-4 [53]. Fig. 9b shows similar simulated data to the Fig. 9a, or less than unity values of effective permittivity and reveals the great
but also with experimental measurements of permittivity in a 2- potential for using fused-deposition 3D printing in manufacturing
period printed PP and CaTiO3/PP composite coupon in which the novel electromagnetic devices.

Fig. 9. Effect of the dielectric loss on the amplitude of Mie-type resonance. a) Computer simulation of the effective dielectric permittivity in a 2-period striped structure with alternating
ϵl = 2.65 + 0.003i and ϵh = 7.0 + 7.0 * tan δ permittivities. b) The experimental extracted permittivity in a 2-period striped structure of PP + CaTiO3/PP composite (solid curve) and
simulation (dotted curve), using ϵl =2.25+0.0006i and ϵh =5+0.025i.
430 D.V. Isakov et al. / Materials and Design 93 (2016) 423–430

Acknowledgements [25] N.I. Zheludev, Y.S. Kivshar, From metamaterials to metadevices, Nat. Mater. 11
(2012) 917–924.
[26] Y. Liu, X. Zhang, Metamaterials: a new frontier of science and technology, Chem. Soc.
This work was supported by EPSRC Programme Grant QUEST (EP/ Rev. 40 (2011) 2494–2507.
I034548/1). DI expresses thanks to Dr. Majid Naeem (Queen Mary Uni- [27] J. Valentine, J. Li, T. Zentgraf, G. Bartal, X. Zhang, An optical cloak made of dielectrics,
Nat. Mater. 8 (2009) 568–571.
versity London) for useful discussions. [28] K. Edagawa, Photonic crystals, amorphous materials, and quasicrystals, Sci. Technol.
Adv. Mater. 15 (2014) 034805-1–034805-15.
References [29] L. Peng, L. Ran, H. Chen, H. Zhang, J. Kong, T. Grzegorczyk, Experimental observation
of left-handed behavior in an array of standard dielectric resonators, Phys. Rev. Lett.
[1] N. Guo, M.C. Leu, Additive manufacturing: technology, applications and research 98 (2007) 157403-1–157403-4.
needs, Front. Mech. Eng. 8 (2013) 215–243. [30] Z. Zhang, Z. Wang, L. Wang, Design principle of single- or double-layer wave-
[2] W.-C. Lee, C.-C. Wei, S.-C. Chung, Development of a hybrid rapid prototyping system absorbers containing left-handed materials, Mater. Des. 30 (2009) 3908–3912.
using low-cost fused deposition modeling and five-axis machining, J. Mater. Process. [31] C. Caloz, T. Itoh, Electromagnetic metamaterials: transmission line theory and mi-
Technol. 214 (2014) 2366–2374. crowave applications, Wiley-IEEE Press, USA, 2005.
[3] N. Travitzky, A. Bonet, B. Dermeik, T. Fey, I. Filbert-Demut, L. Schlier, T. Schlordt, P. [32] R. Foster, P. Grant, Y. Hao, A. Hibbins, T. Philbin, R. Sambles, Spatial transformations:
Greil, Additive manufacturing of ceramic-based materials, Adv. Eng. Mater. 16 from fundamentals to applications, Philos. Trans. R. Soc. A Math. Phys. Eng. Sci. 373
(2014) 729–754. (2015) 20140365–20140369.
[4] B. Wendel, D. Rietzel, F. Kühnlein, R. Feulner, G. Hülder, E. Schmachtenberg, Additive [33] H. Chen, Metamaterials: constitutive parameters, performance, and chemical
processing of polymers, Macromol. Mater. Eng. 293 (2008) 799–809. methods for realization, J. Mater. Chem. 21 (2011) 6452–6463.
[5] J.F. Rodriguez, J.P. Thomas, J.E. Renaud, Characterization of the mesostructure of [34] Q. Zhao, J. Zhou, F. Zhang, D. Lippens, Mie resonance-based dielectric metamaterials,
fused-deposition acrylonitrile-butadiene-styrene materials, Rapid Prototyp. J. 6 Mater. Today 12 (2009) 60–69.
(2000) 175–186. [35] D.E. Aspnes, Bounds on allowed values of the effective dielectric function of two-
[6] M.E. Pilleux, A. Safari, M. Allahverdi, Y. Chen, Y. Lu, M.A. Jafari, 3D photonic bandgap component composites at finite frequencies, Phys. Rev. B Condens. Matter 25
structures in the microwave regime by fused deposition of multimaterials, Rapid (1982) 1358–1361.
Prototyp. J. 8 (2002) 46–52. [36] A. Sihvola, Mixing rules with complex dielectric coefficients, Subsurf. Sens. Technol.
[7] C.R. Garcia, J. Correa, D. Espalin, 3D printing of anisotropic metamaterials, PIER Lett. Appl. 1 (2000) 393–415.
34 (2012) 75–82. [37] P.S. Grant, F. Castles, Q. Lei, Y. Wang, J.M. Janurudin, D. Isakov, S. Speller, C. Dancer,
[8] A. Kantaros, D. Karalekas, Fiber bragg grating based investigation of residual strains C.R.M. Grovenor, Manufacture of electrical and magnetic graded and anisotropic
in ABS Parts Fabricated by fused deposition modeling process, Mater. Des. 50 (2013) materials for novel manipulations of microwaves, Philos. Trans. R. Soc. A Math.
44–50. Phys. Eng. Sci. 373 (2015) (20140353-14).
[9] K. Wang, Y.-H. Chang, Y. Chen, C. Zhang, B. Wang, Designable dual-material auxetic [38] F. Castles, D. Isakov, A. Lui, Q. Lei, C. E. J. Dancer, Y. Wang, J. M. Janurudin, S. C. Speller,
metamaterials using three-dimensional printing, Mater. Des. 67 (2015) 159–164. C. R. M. Grovenor, and P. S. Grant, Microwave dielectric characterisation of 3D-
[10] P. Nikolaou, A.M. Coffey, L.L. Walkup, B.M. Gust, C.D. LaPierre, E. Koehnemann, M.J. printed BaTiO3/ABS polymer composites, (unpublished).
Barlow, M.S. Rosen, B.M. Goodson, E.Y. Chekmenev, A 3D-printed high power nucle- [39] J. Krupka, A.P. Gregory, O.C. Rochard, R.N. Clarke, Uncertainty of complex permittiv-
ar spin polarizer, J. Am. Chem. Soc. 136 (2014) 1636–1642. ity measurements by split-post dielectric resonator technique, J. Eur. Ceram. Soc. 21
[11] S. Imagawa, K. Edagawa, K. Morita, T. Niino, Y. Kagawa, M. Notomi, Photonic band- (2001) 2673–2676.
gap formation, light diffusion, and localization in photonic amorphous diamond [40] O. Luukkonen, S.I. Maslovski, S.A. Tretyakov, A stepwise Nicolson–Ross–Weir-based
structures, Phys. Rev. B 82 (2010) 115116–115119. material parameter extraction method, IEEE Antennas Wirel. Propag. Lett. 10 (2011)
[12] K.F. Leong, C.M. Cheah, C.K. Chua, Solid freeform fabrication of three-dimensional 1295–1298.
scaffolds for engineering replacement tissues and organs, Biomaterials 24 (2003) [41] O. Sydoruk, E. Tatartschuk, E. Shamonina, L. Solymar, Analytical formulation for the
2363–2378. resonant frequency of split rings, J. Appl. Phys. 105 (2009) 014903–014905.
[13] B.C. Gross, J.L. Erkal, S.Y. Lockwood, C. Chen, D.M. Spence, Evaluation of 3D printing [42] A. Moulart, C. Marrett, J. Colton, Polymeric composites for use in electronic and mi-
and its potential impact on biotechnology and the chemical sciences, Anal. Chem. 86 crowave devices, Polym. Eng. Sci. 44 (2004) 588–597.
(2014) 3240–3253. [43] T. Hu, J. Juuti, H. Jantunen, RF properties of bstpps composites, J. Eur. Ceram. Soc. 27
[14] T. Serra, M.A. Mateos-Timoneda, J.A. Planell, M. Navarro, 3D printed PLA-based scaf- (2007) 2923–2926.
folds, Organogenesis 9 (2014) 239–244. [44] S. Rajesh, K.P. Murali, R. Ratheesh, Preparation and characterization of high permit-
[15] M. Li, R.G. Landers, M.C. Leu, Modeling, analysis, and simulation of paste freezing in tivity and low loss PTFE/CaTiO3 microwave laminates, Polym. Compos. 30 (2009)
freeze-form extrusion fabrication of thin-wall parts, J. Manuf. Sci. Eng. 136 (2014) 1480–1485.
061003–061003-11. [45] A.K. Sood, R.K. Ohdar, S.S. Mahapatra, Parametric appraisal of mechanical property
[16] T.F. McNulty, F. Mohammadi, A. Bandyopadhyay, D.J. Shanefield, S.C. Danforth, A. of fused deposition modelling processed parts, Mater. Des. 31 (2010) 287–295.
Safari, Development of a binder formulation for fused deposition of ceramics, [46] O.S. Es-Said, J. Foyos, R. Noorani, M. Mendelson, R. Marloth, B.A. Pregger, Effect of
Rapid Prototyp. J. 4 (1998) 144–150. layer orientation on mechanical properties of rapid prototyped samples, Mater.
[17] A. Bellini, L. Shor, S.I. Guceri, New developments in fused deposition modeling of ce- Manuf. Process. 15 (2000) 107–122.
ramics, Rapid Prototyp. J. 11 (2005) 214–220. [47] A. Sihvola, Metamaterials in electromagnetics, Metamaterials 1 (2007) 2–11.
[18] M.A. Jafari, W. Han, F. Mohammadi, A. Safari, S.C. Danforth, N. Langrana, A novel sys- [48] B. Slovick, Z.G. Yu, M. Berding, S. Krishnamurthy, Perfect dielectric-metamaterial re-
tem for fused deposition of advanced multiple ceramics, Rapid Prototyp. J. 6 (2000) flector, Phys. Rev. B 88 (2013) 165116-1–165116-7.
161–175. [49] C. Vandenbem, J.P. Vigneron, Mie resonances of dielectric spheres in face-centered
[19] U. Scheithauer, E. Schwarzer, H.-J. Richter, T. Moritz, Thermoplastic 3D printing—an cubic photonic crystals, J. Opt. Soc. Am. A 22 (2005) 1042–1047.
additive manufacturing method for producing dense ceramics, Int. J. Appl. Ceram. [50] B. Du, J. Wang, Z. Xu, S. Xia, J. Wang, S. Qu, Band split in multiband all-dielectric left-
Technol. 12 (2014) 26–31. handed metamaterials, J. Appl. Phys. 115 (2014) 234104–234109.
[20] U. Scheithauer, A. Bergner, E. Schwarzer, H.-J. Richter, T. Moritz, Studies on thermo- [51] M.V. Rybin, I.S. Sinev, K.B. Samusev, A. Hosseinzadeh, G.B. Semouchkin, E.A.
plastic 3D printing of steel–zirconia composites, J. Mater. Res. 29 (2014) 1931–1940. Semouchkina, M.F. Limonov, Photonic properties of two-dimensional high-
[21] A. Bandyopadhyay, K. Das, J. Marusich, S. Onagoruwa, Application of fused deposi- contrast periodic structures: numerical calculations, Phys. Solid State 56 (2014)
tion in controlled microstructure metal–ceramic composites, Rapid Prototyp. J. 12 588–593.
(2006) 121–128. [52] L. Curecheriu, S.-B. Balmus, M.T. Buscaglia, V. Buscaglia, A. Ianculescu, L. Mitoseriu,
[22] S.H. Masood, W.Q. Song, Development of new metal/polymer materials for rapid Grain size-dependent properties of dense nanocrystalline barium titanate ceramics,
tooling using fused deposition modelling, Mater. Des. 25 (2004) 587–594. J. Am. Ceram. Soc. 95 (2012) 3912–3921.
[23] M. Nikzad, S.H. Masood, I. Sbarski, Thermo-mechanical properties of a highly filled [53] P. Hu, H. Jiao, C.-H. Wang, X.-M. Wang, S. Ye, X.-P. Jing, F. Zhao, Z.-X. Yue, Influence of
polymeric composites for fused deposition modeling, Mater. Des. 32 (2011) thermal treatments on the low frequency conductivity and microwave dielectric
3448–3456. loss of CaTiO3 ceramics, Mater. Sci. Eng. B 176 (2011) 401–405.
[24] M. Trunec, J. Cihlar, Thermal removal of multicomponent binder from ceramic injec-
tion mouldings, J. Eur. Ceram. Soc. 22 (2002) 2231–2241.