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Journal of Magnetism and Magnetic Materials 323 (2011) 2064–2069

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Journal of Magnetism and Magnetic Materials


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

Bioinspired fabrication of magneto-optic hierarchical architecture by


hydrothermal process from butterfly wing
Wenhong Peng, Xiaobin Hu n, Di Zhang n
State Key Lab of Metal Matrix Composites, Shanghai Jiao Tong University, Shanghai 200240, People’s Republic of China

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

Article history: We developed a green solution to incorporate nano-Fe3O4 into the hierarchical architecture of a natural
Received 21 December 2010 butterfly wing, thus obtaining unique magneto-optic nanocomposites with otherwise unavailable
Received in revised form photonic features. Morphological characterization and Fourier Transform Infrared–Raman Spectroscope
8 March 2011
measurements indicate the assembly of Fe3O4 nanocrystallites. The magnetic and optical responses of
Available online 12 March 2011
Fe3O4/wing show a coupling effect between the biological structure and magnetic material. The
Keywords: saturation magnetization and coercivity values of the as-prepared magneto-optic architecture varied
Bioinspired with change of subtle structure. Such a combination of nano-Fe3O4 and natural butterfly wing might
Hydrothermal process create novel magneto-optic properties, and the relevant ideas could inspire the investigation of
Magnetite
magneto-optical devices.
Hierarchical architecture
Crown Copyright & 2011 Published by Elsevier B.V. All rights reserved.

1. Introduction atomic layer deposition, sol–gel process, and hydrothermal pro-


cess, respectively. However, to the best of our knowledge, little
Biological structures on the external surfaces of animals, work has been done for combine magnetite with butterfly wings.
insects, and plants are remarkably sophisticated, with amazing As a natural magnetic material, magnetite (Fe3O4) has attracted a
abilities to perform multiple functions and comply with numer- great deal of research interest due to its extensive applications in
ous, often conflicting demands. For example, adhesive force various fields, such as biomedicine [15], catalysts, high density
provided by gecko foot-hairs [1,2], self-cleaning effect on the magnetic recording media, and medical diagnosis [16]. Inoue
lotus leaves [3], and the striking optical effects caused by et al. [17] reported that one-dimensional magneto-photonic crystals
beetles [4], are all related to the unique micro- and nanostruc- composed of dielectric and magnetic materials exhibit remarkable
tures on the surfaces [5–7]. Inspired by nature, these fascinating magneto-optical properties accompanied by a huge enhancement in
structures have been employed as templates to create exquisite their Kerr and Faraday rotations,and giant enhancement of nonlinear
replicas from a variety of metal oxides and noble metals. magneto-optical response [18] was observed. The magneto-optical
Butterfly wing is one of the best examples, which owns the effect is crucial, which determines the read-write speed of the
largest number of species and each species possess the unpar- magnetic recording materials [19] and sensitivity of the magnetic
alleled structure and color. The wings are made of small scales switch [20]. A series of natural photonic crystals based on natural
forming two or more layers over the wing membrane like roof- butterfly was reported [9,21], where it was shown that natural
tiles [8]. The subtle microstructures of the scales form two main butterfly wings have unique features that modulate visible light. In
optical effects, multi-layers that produce thin-film interference comparison with known natural photonic crystals, we consider
colors and lattices that produce diffraction colors. Studies show magnetic material with natural photonic crystals more effective
that iridescent butterfly scales are structurally colored, relying because their photonic properties are sensitive to magnetic and
upon the interaction of light with detailed architecture to produce electric fields and they have the potential for use in a variety of
their color [9]. The diversity of colors and subtle hierarchical optoelectronic devices.
structures on the butterfly wing boom the biotemplating inves- Herein, two species of butterflies with different wing scale
tigation. In 2003,Cook et al. [10] synthesis silica wing by chemical patterns are chosen as template for the fabrication of magnetite
vapor deposition. Later, phosphor wing [11], ZnO microtube magneto-optic architecture. We studied two conventional bio-
wing [8,12], Al2O3 hollow wing [9], SnO2 wing [13], and CdS/ template oxide synthesis routes for magnetite architecture fabri-
wing [14] were developed using solution casting, dipping process, cation: Air Oxidation Method (AOM) and Vacuum Reduction
Method (VRM). However the oxidation of ferrous ion in atmo-
sphere can be hardly control in AOM and the adsorption ferric ion
n
Corresponding author. in ethylene glycol solution is extremely low. On the basis of
E-mail addresses: hxb@sjtu.edu.cn (X. Hu), zhangdi@sjtu.edu.cn (D. Zhang). summarizing the failed experiences, we present a significant

0304-8853/$ - see front matter Crown Copyright & 2011 Published by Elsevier B.V. All rights reserved.
doi:10.1016/j.jmmm.2011.03.015
W. Peng et al. / Journal of Magnetism and Magnetic Materials 323 (2011) 2064–2069 2065

advance on the up two method using ferrous sulfate heptahydrate 2.3. Sample characterization
as the only iron source and hydrogen peroxide as the oxidant. We
develop the one-step synthesis of hierarchical microstructures of The as-synthesized samples were examined by FTIR measure-
magnetite magnetic optical architecture from butterfly wing via ments using a Bruker EQUINOX 55 instrument. X-ray diffraction
Hydrothermal Method (HM). The as-synthesized sample exhibits (XRD) measurements were carried out with a Bruker-AXS X-ray
increase magnetic properties with the ultrafine structure. Since diffractometer system by applying CuKa radiation. The investiga-
hierarchy porous structure could participate in tuning nano-Fe3O4 tions of the morphologies and microstructures of the products were
magneto-optical properties, the combination of nano-Fe3O4 and carried out using a FESEM (FEI XL30). The FESEM was operated
wing scales would be promising and significant. This investiga- under 5.0 kV (Acc.V). Transmission electron micrographs (TEM),
tion may also provide helpful information for the synthesis of high-resolution transmission electron micrographs (HRTEM), and
other magnetic materials with peculiar structures. selected area electron diffraction (SAED) patterns were obtained on
a JEOL JEM-2100F instrument. Reflection spectra were measured on
a UV spectrometer (Cary 500) and an integrating sphere. The
2. Experimental magnetization measurements were performed using a Vibrating
Sample Magnetometer (VSM, Lakeshore 7407) at room temperature
2.1. Materials to investigate the magnetic properties.

The butterfly wing scales chosen as biotemplates are butterflies


3. Results and discussion
Euploea mulciber (subfamily Danainae of the family Danaidae)
and Papilio paris (subfamily Papilioninae of the family Papilioni-
According to the thermodynamics of Fe3O4 synthesis, a complete
dae), which were purchased from a butterfly garden in Shanghai.
precipitation of Fe3O4 takes place when a molar ratio of Fe3 þ :Fe2 þ is
All reagents used in this experiment were of analytical grade
2:1. As ferrous ions can be easily oxidized in air, scientists adopted
without further purification.
various protective measures in the process of synthesis Fe3O4, such
as feeding with inert atmosphere [23], annealing under vacuum [24],
2.2. Fabrication process and using poisonous as protective layer [25]. Herein, we tried three
different harmless and environmentally friendly methods for the
We developed three different methods for the fabrication of preparation of magnetic wings.
magnetic wings as shown in Table 1. In the Air Oxidation Method (AOM), we designed partial oxidized
Air Oxidation Method (AOM): the natural wings were treated by ferrous chloride by air to get magnetite oxide according to the
dipping in 8% NaOH ethanol solution at 60 1C for 1 h, then the work [22]. The X-ray diffraction patterns of the samples heated at
specimen were immersed into a closed vessel containing a different temperature was shown in support information (Figure. S1
solution of the precursor, which were prepared similar to the supporting information). Obviously, there is no Fe3O4 diffraction peaks
work reported in [22], after that, the specimen were heated at the and the samples appears dark brown, which is not consistent with the
temperature range 250–300 1C. results displayed in the work [22]. This may be owing to the instability
Vacuum Reduction Method (VRM): the pre-processing of natural of ferrous chloride, which was gradually oxidized by the air in the 10 h
wings were the same as in the first method. Afterwards, the dipping process. Considering it is hard to control air oxidation, we
treated wings were dipped into 2 mol/L Fe(NO3)3  9H2O ethylene adopted the vacuum environment and cut off the influence of atmo-
glycol solution for 10 h at room temperature, finally the specimen sphere. In the Vacuum Reduction Method (VRM), we seriously control
was annealed at 400 1C under vacuum for 2 h. the ratio of reducing agent and oxidant. We immerse the pre-treated
Hydrothermal method (HM): First, the wings were dipped in an wings into Fe(NO3)3  9H2O ethylene glycol solution for the in situ
activation medium, which was prepared by dispersing ethylene- synthesis of magnetite nanoparticles. As revealed in Fig. 1(a), the
diaminetetraacetic acid (EDTA) in dimethylformamide (DMF) diffraction peaks at 2y ¼35.32, 56.72, and 62.24 were assigned to
with a volume ratio of about 1:10, for 6 h at 110 1C to get the (3 1 1), (5 1 1), and (4 4 0) planes of Fe3O4. The peaks of the spectrum
EDTA/DMF activated wing. Second, FeSO4  7H2O (2.502 g) was in Fig. 1(a) are broadened and it can be explained by the carbon
dissolved in 20 ml deionized water, 10 ml of polyethylene glycol residues and the thin coating layer of magnetite in the final product,
20,000 solution (50 gL  1) was added to the FeSO4  7H2O solution which can be confirmed by the FESEM results show in Fig. 3(b). The
and stirred, followed by 10 ml of diluted ammonia (2.5%). After two routes mentioned above were typical methods for biotemplate
that, 0.27 ml H2O2 was added into the solution slowly while oxide synthesis, unfortunately, the results turned out to be frustrating.
stirring. The mixture was stirred for 5 min to obtain a homo- Remarkably, we demonstrated a novel hydrothermal method based on
geneous solution. The final procedure was carried out as follows: the previous experiment failure to achieve unique magneto-optic
the activated wing was immersed into the above solution, then nanocomposites as shown in scheme 1. In this route, ferrous sulfate
transferred the system into an autoclave, and stored in a sealed heptahydrate was used as the only iron source and hydrogen peroxide
autoclave at 160 1C for 5 h. When finished, the autoclave was as the oxidant, and the aqueous solution provides a golden condition
naturally cooled down to room temperature. The treated wing for preventing oxidation of ferrous ion from air. According to the
was taken out and rinsed thoroughly and dried to harvest the diffraction peaks measured by X-ray diffraction (XRD) exhibited
target sample Fe3O4/wing. in Fig. 1(b), the as-prepared magnetite had a spinel structure with a

Table 1
Procedure factor of different method synthesis magnetic butterfly wing.

Methods Pre-processing Medium ingredients Final treatment

AOM 8% NaOH ethanol solution 60 1C, 1 h 0.1 mol FeCl2  4H2O,0.1 mol citric acid monohydrate, 100 ml ethanol sintering under air
VRM 8% NaOH ethanol solution 60 1C, 1 h 2 mol/L Fe(NO3)3  9H2O ethylene glycol solution vacuum sintering
HM EDTA/DMF 110 1C, 6 h 0.009mol FeSO4  7H2O, 20 ml deionized water, 10 ml of PEG 20000 hydrothermal method
solution (50 gL-1), 10 ml of (2.5%) ammonia 0.27 ml H2O2
2066 W. Peng et al. / Journal of Magnetism and Magnetic Materials 323 (2011) 2064–2069

unit-cell parameter of 0.8396 nm and peaks at 2y ¼29.981, 35.399, standard card (JCPDS no. 19- 0629), The average grain sizes are
43.020, 56.979, and 62.579, can be assigned to (2 2 0), (3 1 1), (4 0 0), calculated to be around 26 nm, according to the Scherrer formula.
(5 1 1), and (4 4 0) planes of Fe3O4, which were identical with the The broadening of the reflection peak also indicates the formation of
the ultrafine nanoparticles. It is known that Fe3O4 can be oxidized to g-
Fe2O3, which can be further transformed into a-Fe2O3 at higher
temperature. The diffraction peaks at (1 1 3), (2 1 0), (2 1 3), and
(2 1 0) are the characteristic peaks of g-Fe2O3, and a-Fe2O3, respec-
tively [26]. Herein, No impurity peaks were detected, indicating the
high purity of main product.
The mechanism of Hydrothermal Method (HM) was studied by
Fourier Transform Infrared–Raman Spectroscope (FTIR) spectrum
in Fig. 2. The natural Butterfly wing presents characteristic bands of
protein and chitin. The absorption bands at 1652 and 1542 cm  1
corresponds to amide I mode (primarily CQO stretch) and amide II
(primarily NH in-plane bend plus CN stretch) [27], respectively. The
bands at 1157, 1114, 1074, and 1029 cm  1 should be assigned to
the vibrational motion of characteristic C–O bonds of chitin. The
band near 1726 cm  1 might be the COOH of glutamic and aspartic
acid residue and the O–H out-plane deformation vibration around
band 950 cm  1 confirm the existence of COOH groups [28]. As
Fig. 1. XRD patterns of the products synthesize through Vacuum Reduction depicted before, the natural wing is treated with EDTA/DMF
Method (a) and Hydrothermal method (b). activation medium to gain more COO– active sites, which is
confirmed by the FTIR results. In detail, OH stretch mode of the
COOH group around 3293 cm  1 (supporting information) decreases
sharply, along with the slight intensification of the 1407 cm  1 band
(COO– stretching) [29]. In the growth stage, the following mechan-
isms of the Fe3O4 nanoparticles embedded into the honeycomb
structure of wing scales were proposed to occur: Fe3O4 nuclei
(nanoparticles) were increasingly formed on the surface of the
substrates. The active sites of substrates (like COO–, O–H) bind
Fe3O4, which is verified by the FTIR results. In the spectrum the new
band at 579 cm  1 corresponded to vibrations of the Fe–O bonds in
the crystalline lattice of magnetite (Fe3O4) [30]. The enhancement
of O–H out-plane deformation vibration (OHyO) near 950 cm-1
indicated magnetite associate with hydrogen bonding of COOH. The
antisymmetric stretching vibration of COO– around 1543 cm  1 is
blueshifted as compared to the activated wing and original wing,
owing to the chelation between the COOH/COO– groups and
magnetite in the final product [31]. Hence, butterfly wings could
be activated by EDTA/DMF suspension to serve as reactive sites and
successive assembly of Fe3O4. Besides, the result of XRD agreed well
with that of the FTIR.
Fig. 2. FTIR spectrum of original wing, activated wing, and final product Fe3O4/ FESEM images in Fig. 3 show the well-organized hierarchical
wing fabricated using HM. cross-ribbing structure of the target product Fe3O4/wing

Fig. 3. FESEM images of natural wing (a,d), final product Fe3O4 architecture obtained by vacuum sintering (b,e), and hydrothermal method (c,d), respectively. (Forewing of
male Euploea mulciber butterflies was used.)
W. Peng et al. / Journal of Magnetism and Magnetic Materials 323 (2011) 2064–2069 2067

synthesized by VRM (b, e), HM (c, f) and the corresponding natural


butterfly wings (a, d). On each scale (Fig. 3(a–c)) the parallel-
aligned ridges and the crossrib comprised periodic grating struc-
ture. A high resolution magnification image (Fig. 3(d–f)) exhibits
the ridges that are piled up stepwise by multi-layer of lamellas.
Such periodic multi-layered structure was assigned to one-dimen-
sional photonic crystal. Comparatively, the final product derived
from the VRM (Fig. 3(b,e)) exhibits thin coating layer of Fe3O4
along with agglomeration nanoparticles distributed heteroge-
neous on the surface of cross-ribbing structure, while the magne-
tite magnetic-optical architecture derived from the HM as
described in Scheme 1, displaying a relatively homogeneous
distribution of thick layer nano-Fe3O4 on the wing scaffolds.
Therefore, Fe3O4 crystallites could be loaded on activated butterfly
wings without destroying the photonic crystal structures by HM.
Details of the Fe3O4 architecture synthesized using HM was
studied by TEM analyses (Fig. 4). To prepare the TEM sample, the
specimen was smashed by ultrasonic for 3 h in ethanol. Fe, O, and C
elements were detected using an EDX accessory, corresponding to the
Fe3O4 coating and the protein/chitin components of the natural wing.
It is noteworthy that the existence of Fe3O4 in the fragments should
be due to the chemical bonding between Fe3O4 and wing, as revealed
by the previously mentioned FTIR results. The size and morphology of
cross-ribbing structure was comparative to the FESEM results, the Fig. 4. Medium- and high-resolution transmission electron microscopy images of
dotted yellow line in Fig. 4(a) delineated the structure more clearly. cross-ribbing structure magnetite (a–c). The dotted line delineated the cross-
The TEM results indicating the as-prepared Fe3O4 coating is mainly ribbing structure legibly in (a). (d) EDX results.
constructed by spinel Fe3O4 nanocrystallites with diameter of 20–
30 nm, which agreed well with the XRD measurement.
The loading of Fe3O4 on butterfly wings can be observed by
naked eyes as shown in Fig. 5. The natural forewing of male butterfly
Euploea mulciber exhibits a shining violet blue color, which should
correspond to its photonic crystal structure [14]. The final product
turned to black (synthesized using VRM) and black blue (synthe-
sized using HM), respectively. This should be attributed to the
change of photonic crystal parameters (e.g. refractive index and
lattice distance). After the VRM process, the sample was composed
of carbon coating with magnetite other than chitin and nano-Fe3O4
composite. Due to the vacuum annealing, the grating structure was
preserved faithfully. The optical response characteristics of the
natural butterfly wing and that of the Fe3O4 composite were
determined by measuring their corresponding reflectance spectra
in visible and near-infrared regions. The incident angle is vertical to
Fig. 5. (left) reflectance spectra of natural butterfly wing (a), tFe3O4/wing using
the surface of the substrate. Fig. 5 presents the reflection VRM (b), Fe3O4/wing using HM; (right) photographs of natural wing (a), VRM
synthesized wing (b), and HM synthesized wing; (Forewing of male Euploea
mulciber butterflies was used).

measurement results, where Fig. 5(b) shows the results of Fe3O4/


wing from VRM and Fig. 5(c) is the one produced using HM. The
reflectance spectrum of the natural butterfly wings is listed for
comparison in Fig. 5(a). The natural wing has a strong reflection
peak around 410 nm, indicating the existence of a photonic band
gap (PBG) in the natural structure [32]. It should be noted that the
pigments contained in natural butterfly wings can affect the
reflectance spectra [33]. Fig. 5(b) reveals two reflection peaks
around 450 and 580 nm, while Fig. 5(c) exhibit same reflection
peak around 410 nm compare to the natural wing along with a new
enhancement reflection peak at 690 nm. In comparison to the
natural butterfly wing, low reflectance of the final product wings
lead to the characteristic black appearance. The particular colors of
the butterfly wings and the replica are mainly due to the optical
interference involving a grating structure (lamellae) and a pseudo-
photonic crystal (cross-ribbing structure). Shrinkage of the struc-
tures yielded new steam bread peaks. To Fig. 5(b) the first reflection
peak is redshifted as relative to natural butterfly wing, owing to the
Fe3O4 carbon wing composite having an index of refraction larger
Scheme 1. Scheme of the procedure used to synthesize Fe3O4/wing composite. than that of natural wing materials. Since the PBG may shift to long
2068 W. Peng et al. / Journal of Magnetism and Magnetic Materials 323 (2011) 2064–2069

wavelength ranges with the increase in the materials’ reflective The magnetic properties of the Fe3O4/wing (Fig. 7(a)) synthesized
index, present results are quite reasonable. The reflection peak at using VRM and the quasi-honeycomb like magnetite (Fig. 7(b)),
410 nm implied that the HM synthesized magnetite architecture cross-ribbing magnetite (Fig. 7(c)), and Fe3O4 nanoparticles
(Fig. 4(c)) inherits the optical response of natural wing. Besides, we
attribute the slight enhancement reflection peak of Fe3O4 architec-
ture composite around 690 nm to the change of optical parameters
(refractive index and lattice distance). Relative to natural wing, the
lattice distance of the magneto-optic architecture with a coating
layer of nano-Fe3O4 was decreased, and the surface of the final
product is much rougher. The rougher surface can enhance scatter-
ing, which also explain the low reflectance of the magnetite
architecture.
Research shows that the patterns of magnetic materials are
essential to their magneto-optic properties. Herein, another type of
wing scales with different patterns is applied to mediate the
assembly of nano-Fe3O4. Fig. 6(d–f) present the quasi-honey comb
like magnetite architecture corresponding to the natural Papilio paris
butterfly wings (Fig. 6 (a–c)).The natural Papilio paris butterflies
show the well-organized quasi-honeycomb structure, the porous is
consisted from micrometer down to 300 nm. The direct evidence of
the formation of Fe3O4 nanoparticles coating on natural butterfly
wing is given in Fig. 6(d–f). It is apparent that Fe3O4 nanoparticle is
homogeneous coated on the subtle structure of Papilio paris butter- Fig. 7. Magnetization loops of Fe3O4/wing (a) synthesized using VRM, quasi-
flies and the porous of final product is slight smaller compared to the honeycomb like magnetite (b), cross-ribbing magnetite (c), and Fe3O4 nanoparticles
natural butterfly wing because of the coating layer. (d) prepared using HM.

Fig. 6. FESEM images of natural wing (a–c) and final product Fe3O4/wing (d–f) obtained using a typical procedure as described in the experimental section. (Forewing of
male Papilio paris butterflies was used.)
W. Peng et al. / Journal of Magnetism and Magnetic Materials 323 (2011) 2064–2069 2069

Table 2
Magnetic characteristics of samples with different morphologies.

Sample Ms (emug) Hci (Oe) Size (nm) Reference

Fe3O4 nanoparticle 71.95 94.5 26 Inour work


Fe3O4 cross-ribbing structure 30.94 118.6 26 In our work
Fe3O4 quasi-honeycomb structure 19.31 121.3 26 In our work
Fe3O4 nanoparticle 81.0 97.5 37 [34]
Fe3O4 fibrous nanostructure 35.2 – Diameter 20 [35]
Fe3O4 nanowires 68.7 – diameter 35–100 [35]

(Fig. 7(d)) synthesized using HM measured at room temperature are Shanghai University School and Materials Science and Engineering
illustrated in Fig. 7. The hysteresis loop of samples shows a ferro- for Magnetization loops measurement, Qin Hong from State Key Lab
magnetic behavior with saturation magnetization of 7.794, 19.313, of Metal Matrix Composites for XRD measurement, and SJTU
30.939, and 71.955 emu/g and coercivity of 117.18, 121.26, 118.58, Instrument Analysis Center for FESEM and FTIR measurements.
and 94.532 Oe, respectively. The saturation magnetization of Fe3O4/
wing is much lower than Fe3O4 nanoparticles, while the Ms of the
Fe3O4 nanoparticles were consistent with the reported values [34] Appendix A. Supporting information
(Table 2). Although the source of low saturation magnetization is
not clear, the chitin scaffold in the samples and specific structures Supplementary data associated with this article can be found
preventing Fe3O4 nucleus from magnetizing in directions other than in the online version at doi:10.1016/j.jmmm.2011.03.015.
along their easy magnetic axes [35], might be two major reasons.
Besides the coercivity of sample c is much higher than sample b
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