NiâCuâP Metallic Glass ... - ACS Publications

Research Article www.acsami.org

Thin and Flexible Fe−Si−B/Ni−Cu−P Metallic Glass Multilayer Composites for Efficient Electromagnetic Interference Shielding Jijun Zhang,†,‡,§ Jiawei Li,*,†,‡ Guoguo Tan,†,‡ Renchao Hu,†,‡ Junqiang Wang,†,‡ Chuntao Chang,∥ and Xinmin Wang†,‡ †

Key Laboratory of Magnetic Materials and Devices, Ningbo Institute of Materials Technology & Engineering and ‡Zhejiang Province Key Laboratory of Magnetic Materials and Application Technology, Chinese Academy of Sciences, Ningbo 315201, China § University of Chinese Academy of Sciences, Beijing 100049, China ∥ Dongguan University of Technology, Dongguan 523808, China S Supporting Information *

ABSTRACT: Thin and flexible materials that can provide efficient electromagnetic interference (EMI) shielding are urgently needed, especially if they can be easily processed and withstand harsh environments. Herein, layer-structured Fe− Si−B/Ni−Cu−P metallic glass composites have been developed by simple electroless plating Ni−Cu−P coating on commercial Fe−Si−B metallic glasses. The 0.1 mm-thick composite shows EMI shielding effectiveness of 40 dB over the X-band frequency range, which is higher than those of traditional metals, metal oxides, and their polymer composites of larger thickness. Most of the applied electromagnetic waves are proved to be absorbed rather than bounced back. This performance originates from the combination of a superior soft magnetic property, excellent electrical conductivity, and multiple internal reflections from multilayer composites. In addition, the flexible composites also exhibit good corrosion resistance, high thermal stability, and excellent tensile strength, making them suitable for EMI shielding in harsh chemical or thermal environments. KEYWORDS: Fe-based metallic glasses, electroless Ni−Cu−P, multilayer composites, electromagnetic shielding, harsh environments

1. INTRODUCTION Electromagnetic interference (EMI) or electromagnetic radiation created by commercial and military electronic devices has led to significant concerns regarding electromagnetic pollution. To mitigate the detrimental impacts of EMI on device performance and human health, much effort has been devoted to exploring materials that can provide high shielding efficiency over a wide range of frequencies. Especially, searching for EMI shielding materials with light weight, flexibility, good thermal stability, high strength, corrosion resistance, and that are easy to fabricate has become a hot research area.1−8 However, the fabrication of EMI shielding materials with the above characteristics remains a great challenge. Generally, an effective EMI shielding material should be electrically conductive.1,2 Conductive polymer composites (CPCs) are of great interest for combating EMI interference, owing to their ultrahigh conductivity, flexibility, and low densities. For example, polymer−matrix composites embedded with carbon nanotubes or graphene showed shielding effectiveness (SE) values of 20−80 dB.5−9 Additionally, according to the classical skin effect equation, apart from conductivity, absorption loss (skin depth) is also a function of relative permeability.10,11 Thus, soft magnetic constituents © 2017 American Chemical Society

(Fe3O4, Fe2O3) were doped into CPCs, contributing to high EMI SE and thermal stability.12−19 But, CPCs exhibit drawbacks like severe delamination/agglomeration of fillers and poor adhesion between layers, and their shielding effectiveness is intimately related to the doping concentration.2,10,12 Recently, extreme shielding capabilities (50−92 dB) were reported in MXenes with thickness ranging from 2.5 to 45 μm, deemed as a sparkling star for EMI shielding.1 Yet this two-dimensional material is only limited to theoretical and experimental research, far from practical application. In contrast, traditional metals and metal-based composites are the most common materials used to screen electromagnetic waves (EMWs).20−31 Metals, like copper,20 aluminum,21 and silver,22,23 primarily account for high-frequency EMI shielding due to their superhigh electrical conductivity and glorious anticorrosion performance. Whereas, static or tardily varying magnetic fields are generally screened by high magnetic permeability metals, including pure iron, silicon steel,29 Fe− Al alloy,30 and permalloy, regardless of their low corrosion/ Received: August 20, 2017 Accepted: November 10, 2017 Published: November 10, 2017 42192

DOI: 10.1021/acsami.7b12504 ACS Appl. Mater. Interfaces 2017, 9, 42192−42199

Research Article

ACS Applied Materials & Interfaces

Figure 1. Fabrication, characterization, and composition distribution of the layer-structured FNMG ribbons via electroless plating. (a) Schematic fabrication process of the FNMG ribbons, including sensitization, activation, and electroless plating. (b) Photograph of FNMG ribbons shaped into different shapes, showing exceptional flexibility. (c, d) Surface morphologies of the Fe−Si−B and FNMG-5 samples, respectively. (e) Cross-section image and (f−k) elemental distribution images of the FNMG-5 ribbon. (l) Schematic illustration of the FNMG multilayer composite made of five ribbons, forming a uniform plane with thickness of about 0.1 mm.

oxidation resistance. Yet, the high density, poor flexibility, and restricted tuning in shielding bandwidth of the metals have limited their application primarily to small devices and components.2 Among the various metallic materials, Fe-based metallic glasses and nanocrystalline alloys have been considered as highly efficient and flexible magnetic shielding materials due to their outstanding soft magnetic properties.32,33 Unfortunately, the poor conductivity limits their use in high-frequency EMI shielding.34−36 It is known that electroless Ni-based coatings have been widely used in the electronics industries because of their appealing conductivity, high EMI SE, easy processability, and excellent corrosion resistance.37−39 For example, Ni−P plated polyester fabric exhibited EMI SE of more than 60 dB.38,39 However, the thickness of these electroless Ni-based coatings was relatively large to obtain high EMI SE, seriously deteriorating the flexibility of the coatings. Here, we reported highly thin and flexible Fe−Si−B/Ni− Cu−P metallic glass (FNMG) multilayer composites with excellent EMI shielding performance. The layer-structured shields were made by electroless plating a Ni−Cu−P amorphous coating onto the Fe−Si−B metallic glass substrate (Figure 1). The 5 min electroless composite (0.1 mm), in particular, showed high a EMI SE of 40 dB. These metallic glass multilayer composites possessed additional advantages such as mechanical flexibility, easy processing, good corrosion resistance, high thermal stability, and excellent tensile strength. This finding suggests that the metallic glass, with excellent electrical conductivity, good magnetic properties, and multiple internal

reflections, is a potential candidate for efficient EMI shielding in harsh chemical and thermal environments.

2. EXPERIMENTAL SECTION 2.1. Synthesis of Fe−Si−B/Ni−Cu−P Metallic Glass (FNMG) Multilayer Composites. Fe78Si9B13 metallic glass ribbons (ATM Co. Ltd) of 150 mm width and about 19 μm thicknesses were used as the substrates. Electroless Ni−Cu−P coating was performed by multistage processes comprising sensitization, activation, Ni−Cu−P deposition, and post-treatment of rinsing and drying (Figure 1a). Surface sensitization was conducted by immersing the ribbons into an aqueous solution that contains 10 g/L SnCl2 and 40 mL/L 38% HCl at 298 K for 2 min. Subsequently, the specimens were rinsed with deionized water and activated via immersion into a solution containing 0.5 g/L PdCl2 and 10 mL/L 38% HCl at 298 K for 2 min. Then, the specimens were washed with large volumes of deionized water to prevent the plating bath from contamination. Finally, the specimens were immersed into the electroless Ni−Cu−P plating bath for a certain time. After deposition, the samples were thoroughly rinsed with absolute ethyl alcohol several times to remove the reaction solutions, and then they were dried in air. The CuSO4·5H2O concentration in the electrolyte applied was 1 g/L, and the electroless plating times were 5, 10, and 15 min, respectively. The temperature and pH of the electrolyte were maintained at 363 K and 5−6, respectively. The composition of the electroless Ni−Cu−P plating bath is listed in Table S1 (Supporting Information). 2.2. Material Characterization. Both plan-view and cross-section morphologies of the layer-structured samples were examined with scanning electron microscopy (SEM), and chemical compositions were measured by energy-dispersive X-ray spectroscopy. The amorphous structure of the as-prepared samples was confirmed by X-ray diffraction (XRD) equipped with Cu Kα radiation. 42193


Research Article


Figure 2. Magnetic and electric properties of the Fe−Si−B and FNMG ribbons at room temperature. (a) Hysteresis loops. (b) Variation of conductivity. The inset in (a) shows the magnified high-field region.

Figure 3. EMI SE of the Fe−Si−B and FNMG multilayer composites. (a) SE total, (b) SE absorption, and (c) SE reflection of the Fe−Si−B (black square), FNMG-5 (red circle), FNMG-10 (green rhombus), and FNMG-15 (blue triangle) composites as a function of frequency in 8−12 GHz (Xband). (d) Total EMI SE (SET), absorption (SEA), and reflection (SER) calculated at 10 GHz. The dash lines are guides for eyes. 2.3. Material Measurements. Magnetic properties including saturation magnetization (Ms), coercivity (Hc), and initial permeability (μi) were measured using a vibrating sample magnetometer (VSM) with an applied field of 800 kA/m, a direct current B−H loop tracer at a field of 800 A/m, and an impedance analyzer under a field of 1 A/m, respectively. The electrical conductivity was measured using a standard four-probe method on a Napson Cresbox Measurement System. The EMI SE test was carried out at room temperature in the frequency range of 8−12 GHz using a vector network analyzer (Agilent N5234A). The 0.1 mm thick multilayer composites were made of five layers of Fe−Si−B/Ni−Cu−P ribbons (Figure 1l). The ribbons were cut into rectangle plates with a dimension of 22.8 × 10.2 mm2 to fit the waveguide sample holder. Then, five plates were superposed together and the nonconductive glue was attached to the composite borders. A nonconductive gasket was used as a carrier to mount the composite shield onto the sample holder, to prevent microwave leakage from the borders. Corrosion resistance measurement was conducted by an electrochemical workstation (Zahner Zennium) in aerobic 3.5 wt % NaCl solution at room temperature. The thermal stability of the ribbons was studied by differential scanning calorimetry (DSC)

measurement at a heating rate of 40 K/min. The tensile strength of the ribbons was measured using an Instron testing machine at a constant strain rate of 1 × 10−4 s−1. The tape test40 was performed by pasting scotch tape on the surface of the coating under a pressure of 1000 N. Then, the tape was stripped away manually to confirm whether the residual Ni−Cu−P coating was glued to the tape.

3. RESULTS AND DISCUSSION The Fe−Si−B/Ni−Cu−P metallic glass (FNMG) ribbons were fabricated by electroless plating Ni−Cu−P coating onto the Fe−Si−B metallic glass substrate through two simple pretreatments and followed by an electroless plating process, as described schematically in Figure 1a. The FNMG ribbons with electroless plating times of 5, 10, and 15 min were conveniently labeled as FNMG-5, FNMG-10, and FNMG-15, respectively. The FNMG ribbons could be easily manufactured in a largearea, twisted, and even folded into special shapes due to their mechanical flexibility (Figure 1b). Besides, the FNMG ribbons exhibit good bonding strength between the Ni−Cu−P coating 42194


Research Article


FNMG-5 sample with relative weak conductivity exhibits the highest EMI shielding performance. This is contrary to the Schelkunoff theory wherein the higher the conductivity, the better the EMI shielding performance.42 Similar results were also reported for magnetic CPCs and yolk−shell microwave absorption composites. Instead of optimizing the EMI SE, overdoping of magnetic particles into the conductive matrix resulted in a drop of the EMI SE.12,15,17 In a yolk−shell Ni@ void@SnO2 (Ni3Sn2) ternary system, the composites with high conductivities exhibited weak electromagnetic (EM) wave absorption ability.43 The analysis of SE absorption (SEA) and SE reflection (SER) indicates that the enhancement of total SE (SET) in the FNMG samples mainly comes from the contribution of SEA, as much higher SEA values are observed for the deposited samples (Figure 3b,c). To gain a clearer picture, the corresponding SET, SEA, and SER values at 10 GHz are given in Figure 3d. A distinct transition from a reflection- to absorption-dominant EMI shielding mechanism is detected. For Fe−Si−B metallic glass, reflection is the primary shielding mechanism, which is consistent with the previous understanding that the EMWs are often attenuated by reflection when they strike at the smooth surface of the metals.2,10 Whereas for the FNMG multilayer samples, absorption is responsible for the high EMI SE in preference to reflection, due to their strengthened electrical conductivity. Moreover, both SER and SEA reach the maximum value for the FNMG-5 multilayer sample. That is, electroless plating for 5 min is the optimum process. In Figure 3d, SEA is sensitive to the electroless plating time, whereas SER remains nearly constant. This phenomenon may originate from the following factors: first, the competition between conductivity and the rough surface of the FNMG samples. Reflection depends upon the conductivity of the shields and correlates to the impedance mismatch between the air and the shields. The growing of free charge carriers (electrons or holes) at the surface is assumed to increase the reflection of EMWs.44 However, compared with the smooth surface of the Fe−Si−B metallic glass (Figure 1c), the nacre-like surface in FNMG (Figure 1d) is beneficial for providing a lot of point receivers to allow more EMWs to enter into the shields, rather than reflect back.45 Second, the relative complex permittivity (εr = ε′ − jε″) and permeability (μr = μ′ − jμ″) measured in Figure S7 indicate that the FNMG-5 sample has the best impedance matching among the four samples, which is favorable for the increment of microwave attenuation.46 Besides, the ε″ values of the FNMG-5 and FNMG-10 samples are higher than those of the Fe−Si−B and FNMG-15 samples, suggesting a large amount of energy dissipation.45 Third, the enhanced EMI shielding performance of FNMG-5 is a result of the balance between the magnetic and electrical properties. As shown in Figure S8, a balance between high initial permeability and high conductivity is obtained in FNMG samples when the electroless plating time is around 5 min. This trend suggests a stronger magnetic/electrical interaction and an enlarged interfacial and contact resistance for EMW attenuation.17 Thus, the variation of SET is mainly due to the competition between the improved conductivity and rougher surfaces, and the balance between magnetic and electrical properties of the samples. According to Kong47 and Sarto,48 the EMI shielding mechanism of a multilayer shield should be explained through the physical properties layer by layer. As described in Figure 1, the FNMG ribbons contain a couple of Ni−Cu−P coatings and

and Fe−Si−B substrate, because no residual Ni−Cu−P coating could be seen on the tape (Figure S1). The broad diffuse X-ray peaks (Figure S2) confirm the amorphous nature of all FNMG ribbons. To demonstrate the morphologies and structures of the FNMG ribbons, field-emission scanning electron microscopy was employed. The pristine Fe−Si−B metallic glass ribbons show a smooth surface, whereas the as-synthesized FNMG-5 ribbons exhibit a much rougher and typical nacre-like surface; neither pores nor cracks were detected on the surfaces (Figure 1c,d). The cross-sectional SEM image and elemental mappings of the FNMG-5 ribbon are shown in Figure 1e−k. The Ni−Cu−P coating with thickness of around 400 nm adhered uniformly to the surface of the Fe−Si−B substrate. Energy-dispersive X-ray spectrometry characterization further reveals the existence and homogeneous distribution of the Ni, Cu, and P elements, confirming that the Ni−Cu−P coating has been well synthesized on the surface of the Fe−Si−B metallic glass. B element observed in the Ni−Cu−P coating (Figure 1h) is caused by a matrix effect. The study on the crystallization and boron distribution of CoFeB/MgO/CoFeB showed that B could diffuse easily through the Ni-based capping layer.41 A schematic illustrating the structural characterization of the FNMG ribbon and composite is given in Figure 1l. The multilayer composite was made of five ribbons forming a uniform plane with thickness of about 0.1 mm. Each layer contains a couple of Ni−Cu−P coatings and one Fe−Si−B ribbon in the middle, forming a conductive layer/permeable magnetic layer/conductive layer structure. Figure 2a shows the M−H hysteresis loops of the Fe−Si−B and FNMG ribbons at room temperature. A summary of the magnetic and electric properties of the FNMG ribbons is listed in Table S2. All of the ribbons exhibit a slender hysteresis loop (Figure 2a), low coercivity, and high permeability (Figure S3), which is characteristic of excellent soft magnetic behaviors. The pristine Fe−Si−B ribbon exhibits a saturation magnetization (Ms) of 178 emu/g and the Ms of the FNMG-5, FNMG-10, and FNMG-15 ribbons are 172, 167, and 162 emu/g, respectively. The slight deterioration in soft magnetic performance may due to the amount of nonmagnetic Ni−Cu−P addition. On the other hand, with increasing deposition time, the Ni−Cu−P coating induces an increment in conductivity, reaching 10.8 × 105 S/m for the FNMG-15 ribbon (180 000 S/ m higher than that of the Fe−Si−B ribbon). However, a longer deposition time (i.e., 30 and 60 min) decreases significantly Ms and also causes cracks in the surface of the Ni−Cu−P coating (Figures S4b and S5c−f), thus deteriorating the soft magnetic properties and flexibility of the FNMG ribbons. To explore the EMI shielding performance, the Fe−Si−B and FNMG multilayer composites with a dimension of ∼22.8 mm × 10.2 mm × 0.1 mm were measured using the waveguide measurement set up in the frequency of 8−12 GHz (X-band). As shown in Figure 3a, the Fe−Si−B multilayer sample exhibits an EMI SE value of less than 10 dB and Aeff values from 0.44 to 0.61 (Figure S6), indicating that the EMWs could not be well absorbed. However, the EMI SE value is significantly improved after electroless deposition of the Ni−Cu−P coating onto the surface of the Fe−Si−B substrate. The EMI SE value of 41 dB and the Aeff value of 0.9999 at 10 GHz recorded for the FNMG5 multilayer sample is enough to block 99.99% of incident radiation with only some transmitted (T = 8.06 × 10−5). The EMI SE values of the FNMG-10 and FNMG-15 multilayer samples are just 31 and 16 dB, respectively. Interestingly, the 42195


Research Article


Here, a literature review of common metal materials for EMI SE (Figure 5 and Table S3) clearly indicates that the FNMG

one Fe−Si−B substrate in the middle. In these layer-structured samples, the conductive Ni−Cu−P coatings are expected to generate electric loss, and the soft magnetic Fe−Si−B layer can cause magnetic loss. A feasible mechanism is proposed in Figure 4: (1) EMWs attack the nacre-like surface of the

Figure 5. Comparison of EMI SE with the previous literature and common metal EMI shields in X-band. EMI SE versus thickness of different metal materials. The EMI SE tested in our work is marked by the solid fill-pattern and half solid pattern, and the literature data is marked by an open pattern. A specification of each data point is summarized in Table S3.

Figure 4. Scheme of the EMI shielding mechanism in the FNMG multilayer composites. Incident EM waves (yellow arrows) strike at the surface of the multilayer composite. Some of the EMWs are directly reflected from the highly conducting Ni−Cu−P surface (violet arrows). The remaining EMWs pass through the highly conductive Ni−Cu−P coating and soft magnetic Fe−Si−B substrate, where the EMW energy is attenuated by electric loss (dashed red arrows) and magnetic loss (dashed blue arrows), respectively. At the Ni−Cu−P/ Fe−Si−B interface, the EMWs experience multiple internal reflections (green arrows) and more absorption. Transmitted waves with reduced energy undergo the same process when they come across the next layer. Each time the EMWs pass through a sandwich ribbon, their intensity is noticeably reduced, resulting in the complete elimination of the EMWs.

multilayer composites are pretty good EMI shielding materials. So far, most traditional pure metal and metal-based shielding materials are just limited to copper,20 aluminum,21 silver,22,23 nickel,24,25 stainless steel,21,26 metal oxides,15,19 etc. However, to fulfill common commercial EMI shielding needs (>30 dB),4 large thicknesses (>1 mm) were required. The ultrathin (0.1 mm) and flexible FNMG-5 multilayer composite (SE ∼ 40 dB) obviously outperforms most of the traditional metal-based shields and ranks at the top of the comparison chart. When considering a material’s thickness, EMI shielding effectiveness was divided by sample thickness (SE/t). This thickness-reduced EMI SE was a more realistic parameter to evaluate the effectiveness of different shields. Interestingly, the SE/t value for the FNMG-5 sample is much higher than those of other metal-based materials (Table S3). This finding could open up new application areas for the Fe-based metallic glasses as shielding materials for high-frequency EMWs. In particular, the results indicate that the synergistic effect of good soft magnetic properties, excellent electrical conductivity, and multilayer structure can not only effectively improve the EMI SE of metals but also decrease their thickness, which is needed for good shielding performance. In addition to the outstanding EMI shielding performance, the FNMG multilayer samples also provide good corrosion resistance, high thermal stability, excellent tensile strength, and outstanding mechanical flexibility (Figure 6 and Table S2). The electrochemical measurements of the samples were performed in 3.5 wt % NaCl solution at room temperature (Figure 6a). The pristine Fe−Si−B ribbon shows low corrosion resistance despite the formation of a passive film in the narrow potential range.49 However, notable shifts to more positive potentials are detected for the FNMG ribbons, indicating the Ni−Cu−P coating obviously improves the anticorrosion ability of the FNMG samples. The thermal stability of the FNMG samples was verified by the clear exothermic crystallization peaks that appeared in the DSC traces (Figure 6b). The onset crystallization temperature (Tx) of the three FNMG ribbons is close to that of the pristine Fe−Si−B ribbon (∼795 K), suggesting good thermal stability of the FNMG composite ribbons. The melting temperature (Tm) decreased slightly with

multilayer sample, and then a small amount of EMWs are directly bounced back due to the antagonistic effect between the high conductivity and the rough surface of the Ni−Cu−P coating. (2) The remaining EMWs pass into the highly conductive Ni−Cu−P coating, where electric loss gives rise to a drop in the energy of the EMWs. The high conductivity of the Ni−Cu−P coating causes a conduction loss (Ohmic loss) when the current flows through it and a polarization loss when the dipoles reorient in the alternating EMWs.44 (3) The surviving EMWs encounter the Ni−Cu−P/Fe−Si−B interface. The coexistence of the electric and magnetic phase in the interface induces interfacial polarization and relaxation, which are helpful for EMW energy dissipation.45,46 Meanwhile, the interface behaves as a reflecting surface and leads to multiple reflection and scattering. (4) The EMWs enter into the soft magnetic Fe−Si−B layer, and are further dissipated by magnetic loss that contains hysteresis loss, eddy current effect, natural resonance, and exchange resonance in gigahertz.12,44 (5) Once they have passed through the Fe−Si−B layer, EMWs encounter another Fe−Si−B/Ni−Cu−P interface, and the interactions with the interface repeat. Electric loss is reintroduced by the Ni−Cu−P coating on the other side. The transmitted EMWs with lower energy experience the same absorption process when they strike the next FNMG ribbon. The EMWs can be bounced back and forth between these layers until they are entirely absorbed in the multilayer composite. As a result, the synergetic effects between electric loss, magnetic loss, and interfacial loss are beneficial for the good EMI shielding performance of the FNMG composites. 42196


Research Article


Figure 6. Corrosion resistance, thermal stability, tensile stress, and EMI bending stability of the FNMG shielding materials. (a) Potentiodynamic polarization curves at a scan rate of 1 mV/s in 3.5 wt % NaCl solution. (b) DSC traces at a heating rate of 40 K/min. Tc: Curie temperature; Tx: crystallization temperature. (c) Plots of tensile stress versus strain curve at a strain rate of 10−4 s−1. (d) EMI SE changes of the FNMG-5 multilayer composite in bending test. Inset shows the unfolded (left) and folded multilayer composite (right).

Moreover, the good corrosion resistance, high thermal stability, and excellent mechanical properties of the metallic glass composite allow it to be used in hash environments.

increasing deposition time, proving the existence of the Ni− Cu−P coating on the Fe−Si−B ribbon. In terms of the tensile strength in the longitudinal direction (Figure 6c), the FNMG samples exhibit tensile strength equal to that of the pristine Fe−Si−B ribbons, which is several times higher than those of graphene papers.4,7 Moreover, the FNMG samples exhibit good mechanical flexibility and EMI SE reliability in the bending process. The FNMG-5 composite (22.8 mm × 10.2 mm × 0.1 mm) did not break and crack when it was folded up by tweezers (Figure 6d, inset). Recurrent 100 times bending was operated by hand instead of the tweezers, and no cracks and fissures appeared on the bending surface (Figure S5a,b). It is exciting that the EMI SE values only exhibit slight fluctuations with increasing bending cycles from 10 to 100 times, as shown in Figure 6d. These properties enable the samples to withstand the harsh environments encountered in EMI shielding, and achieve high efficiency and stability in EMI shielding.

■

ASSOCIATED CONTENT

* Supporting Information S

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acsami.7b12504. Measurements of electrical conductivity, electromagnetic interference (EMI) shielding and calculation of skin depth (δ); figures contain the photographs of the tape test, XRD patterns, coercivity plots, conductivity plots, VSM curves, and SEM images of the Fe−Si−B, FNMG30, and FNMG-60 samples; transmission, effective absorption, complex permittivity, and complex permeability plots and initial permeability versus conductivity of the Fe−Si−B and FNMG samples. Tables report chemical composition of the electroless plating bath, summary of electric, magnetic, EMI shielding, thermal stability, and mechanical performance of the FNMG composite and EMI shielding performance of various metal-based shielding materials (PDF)

4. CONCLUSIONS In summary, a facile method to fabricate layer-structured Fe− Si−B/Ni−Cu−P metallic glass composites has been reported, by electroless plating a Ni−Cu−P coating onto the surface of the Fe−Si−B metallic glass. The flexible Fe−Si−B/Ni−Cu−P multilayer composite with a thickness of 0.1 mm simultaneously possesses high electrical conductivity, good soft magnetic properties, and excellent EMI SE (around 40 dB). The reported EMI SE values are highly competitive with common metal shielding materials of much larger thicknesses. The outstanding EMI shielding performance of the metallic glass composite can be attributed to the synergistic effect between the magnetic loss, the electric loss, and the multiple reflections induced by the conductive/magnetic interfaces.

■

AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. Tel: +86-0574-87617212. ORCID

Jiawei Li: 0000-0002-1645-0853 Notes

The authors declare no competing financial interest. 42197


Research Article


■

flexible and light weight composite paper for promising EMI shielding applications. J. Mater. Chem. C 2017, 5, 322−332. (17) Song, W. L.; Guan, X. T.; Fan, L. Z.; Cao, W. Q.; Wang, C. Y.; Zhao, Q. L.; Cao, M. S. Magnetic and conductive graphene papers toward thin layers of effective electromagnetic shielding. J. Mater. Chem. A 2015, 3, 2097−2107. (18) Singh, A. P.; Mishra, M.; Sambyal, P.; Gupta, B. K.; Singh, B. P.; Chandra, A.; Dhawan, S. K. Encapsulation of γ-Fe2O3 decorated reduced graphene oxide in polyaniline core-shell tubes as an exceptional tracker for electromagnetic environmental pollution. J. Mater. Chem. A 2014, 2, 3581−3593. (19) Varshney, S.; Ohlan, A.; Jain, V. K.; Dutta, V. P.; Dhawan, S. K. In Situ Synthesis of Polypyrrole-γ-Fe2O3-Fly Ash Nanocomposites for Protection against EMI Pollution. Ind. Eng. Chem. Res. 2014, 53, 14282−14290. (20) Al-Saleh, M. H.; Gelves, G. A.; Sundararaj, U. Copper nanowire/ polystyrene nanocomposites: Lower percolation threshold and higher EMI shielding. Composites, Part A 2011, 42, 92−97. (21) Li, L.; Chung, D. D. L. Electrical and mechanical properties of electrically conductive polyethersulfone composites. Composites 1994, 25, 215−224. (22) Li, J. P.; Qi, S. H.; Zhang, M. Y.; Wang, Z. F. Thermal conductivity and electromagnetic shielding effectiveness of composites based on Ag-plating carbon fiber and epoxy. J. Appl. Polym. Sci. 2015, 132, No. 42306. (23) Arjmand, M.; Moud, A. A.; Li, Y.; Sundararaj, U. Outstanding electromagnetic interference shielding of silver nanowires: comparison with carbon nanotubes. RSC Adv. 2015, 5, 56590−56598. (24) Gargama, H.; Thakur, A. K.; Chaturvedi, S. K. Polyvinylidene fluoride/nickel composite materials for charge storing, electromagnetic interference absorption, and shielding applications. J. Appl. Phys. 2015, 117, No. 224903. (25) Wenderoth, K.; Petermann, J.; Kruse, K. D.; ter Haseborg, J. L.; Krieger, W. K. Synergism on electromagnetic inductance (EMI) shielding in metal-and ferroelectric-particle filled polymers. Polym. Compos. 1989, 10, 52−56. (26) Ameli, A.; Nofar, M.; Wang, S.; Park, C. B. Lightweight polypropylene/stainless-steel fiber composite foams with low percolation for efficient electromagnetic interference shielding. ACS Appl. Mater. Interfaces 2014, 6, 11091−11100. (27) Shyr, T. W.; Shie, J. W. Electromagnetic shielding mechanisms using soft magnetic stainless steel fiber enabled polyester textiles. J. Magn. Magn. Mater. 2012, 324, 4127−4132. (28) Ma, J.; Wang, K.; Zhan, M. A comparative study of structure and electromagnetic interference shielding performance for silver nanostructure hybrid polyimide foams. RSC Adv. 2015, 5, 65283−65296. (29) Bottauscio, O.; Chiampi, M.; Chiarabaglio, D.; Zucca, M. Use of grain-oriented materials in low-frequency magnetic shielding. J. Magn. Magn. Mater. 2000, 215−216, 130−132. (30) Ma, X.; Zhang, Q.; Luo, Z.; Lin, X.; Wu, G. A novel structure of Ferro-Aluminum based sandwich composite for magnetic and electromagnetic interference shielding. Mater. Des. 2016, 89, 71−77. (31) Sarto, M. S.; Michele, D. S.; Leerkamp, P. Electromagnetic performance of innovative lightweight shields to reduce radiated emissions from PCBs. IEEE Trans. Electromagn. Compat. 2002, 44, 353−363. (32) Chrobak, A.; Kaleta, A.; Kwapulinski, P.; Kubisztal, M.; Haneczok, G. Magnetic Shielding Effectiveness of Iron-Based Amorphous Alloys and Nanocrystalline Composites. IEEE Trans. Magn. 2012, 48, 1512−1515. (33) Haneczok, G.; Wroczyński, R.; Kwapuliński, P.; Chrobak, A.; Stokłosa, Z.; Rasek, J. Electro/magnetic shielding effectiveness of soft magnetic Fe80Nb6B14 amorphous alloy. J. Mater. Process. Technol. 2009, 209, 2356−2360. (34) Haruyama, O.; Annoshita, N.; Nishiyama, N.; Kimura, H. M.; Inoue, A. Electrical resistivity behavior in Pd−Cu−Ni−P metallic glasses and liquids. Mater. Sci. Eng., A 2004, 375−377, 288−291. (35) Haruyama, O.; Annoshita, N.; Kimura, H.; Nishiyama, N.; Inoue, A. Anomalous behavior of electrical resistivity in glass transition

ACKNOWLEDGMENTS This work was supported by the National Key Research and Development Program of China (Grant No. 2016YFB0300500), National Natural Science Foundation of China (Grant Nos. 51501210, 51771215, and 51571207) and Ningbo Municipal Nature Science Foundation (Grant No. 2017A610034).

■

REFERENCES

(1) Shahzad, F.; Alhabeb, M.; Hatter, C. B.; Anasori, B.; Hong, S. M.; Koo, C. M.; Gogotsi, Y. Electromagnetic interference shielding with 2D transition metal carbides (MXenes). Science 2016, 353, 1137− 1140. (2) Thomassin, J. M.; Jérôme, C.; Pardoen, T.; Bailly, C.; Huynen, I.; Detrembleur, C. Polymer/carbon based composites as electromagnetic interference (EMI) shielding materials. Mater. Sci. Eng., R 2013, 74, 211−232. (3) Zhang, Y.; Huang, Y.; Zhang, T. F.; Chang, H. C.; Xiao, P. S.; Chen, H. H.; Huang, Z. Y.; Chen, Y. S. Broadband and tunable highperformance microwave absorption of an ultralight and highly compressible graphene foam. Adv. Mater. 2015, 27, 2049−2053. (4) Yan, D. X.; Pang, H.; Li, B.; Vajtai, R.; Xu, L.; Ren, P. G.; Wang, J. H.; Li, Z. M. Structured Reduced Graphene Oxide/Polymer Composites for Ultra-Efficient Electromagnetic Interference Shielding. Adv. Funct. Mater. 2015, 25, 559−566. (5) Zeng, Z.; Chen, M.; Jin, H.; Li, W.; Xue, X.; Zhou, L.; Pei, Y.; Zhang, H.; Zhang, Z. Thin and flexible multi-walled carbon nanotube/ waterborne polyurethane composites with high-performance electromagnetic interference shielding. Carbon 2016, 96, 768−777. (6) Shen, B.; Zhai, W.; Zheng, W. Ultrathin Flexible Graphene Film: An Excellent Thermal Conducting Material with Efficient EMI Shielding. Adv. Funct. Mater. 2014, 24, 4542−4548. (7) Zeng, Z.; Jin, H.; Chen, M.; Li, W.; Zhou, L.; Zhang, Z. Lightweight and Anisotropic Porous MWCNT/WPU Composites for Ultrahigh Performance Electromagnetic Interference Shielding. Adv. Funct. Mater. 2016, 26, 303−310. (8) Yousefi, N.; Sun, X. Y.; Lin, X. Y.; Shen, X.; Jia, J. J.; Zhang, B.; Tang, B. Z.; Chan, M.; Kim, J. K. Highly aligned graphene/polymer nanocomposites with excellent dielectric properties for high-performance electromagnetic interference shielding. Adv. Mater. 2014, 26, 5480−5487. (9) Wan, S.; Peng, J.; Jiang, L.; Cheng, Q. Bioinspired GrapheneBased Nanocomposites and Their Application in Flexible Energy Devices. Adv. Mater. 2016, 28, 7862−7898. (10) Qin, F.; Peng, H. X. Ferromagnetic microwires enabled multifunctional composite materials. Prog. Mater. Sci. 2013, 58, 183− 259. (11) Chung, D. D. L. Electromagnetic interference shielding effectiveness of carbon materials. Carbon 2001, 39, 279−285. (12) Yang, Y.; Li, M.; Wu, Y.; Wang, T.; Choo, E. S.; Ding, J.; Zong, B.; Yang, Z.; Xue, J. Nanoscaled self-alignment of Fe3O4 nanodiscs in ultrathin rGO films with engineered conductivity for electromagnetic interference shielding. Nanoscale 2016, 8, 15989−15998. (13) Dhawan, R.; Kumari, S.; Kumar, R.; Dhawan, S. K.; Dhakate, S. R. Mesocarbon microsphere composites with Fe3O4nanoparticles for outstanding electromagnetic interference shielding effectiveness. RSC Adv. 2015, 5, 43279−43289. (14) Wu, S.; Zhang, J.; Ladani, R. B.; Ghorbani, K.; Mouritz, A. P.; Kinloch, A. J.; Wang, C. H. A novel route for tethering graphene with iron oxide and its magnetic field alignment in polymer nanocomposites. Polymer 2016, 97, 273−284. (15) Shen, B.; Zhai, W.; Tao, M.; Ling, J.; Zheng, W. Lightweight, multifunctional polyetherimide/graphene@Fe3O4 composite foams for shielding of electromagnetic pollution. ACS Appl. Mater. Interfaces 2013, 5, 11383−11391. (16) Chaudhary, A.; Kumar, R.; Teotia, S.; Dhawan, S. K.; Dhakate, S. R.; Kumari, S. Integration of MCMBs/MWCNTs with Fe3O4 in a 42198


Research Article

ACS Applied Materials & Interfaces region of a bulk Pd40Ni40P20 metallic glass. J. Non-Cryst. Solids 2002, 312−314, 552−556. (36) Stokłosa, Z.; Rasek, J.; Kwapuliński, P.; Badura, G.; Haneczok, G.; Pająk, L.; Lelątko, J.; Kolano-Burian, A. Magnetic, electrical and plastic properties of Fe 76 Nb 2 Si 13 B 9 , Fe 75 Ag 1 Nb 2 Si 13 B 9 and Fe75Cu1Nb2Si13B9 amorphous alloys. J. Alloys Compd. 2011, 509, 9050−9054. (37) Zhang, W. X.; Jiang, Z. H.; Li, G. Y.; Jiang, Q.; Lian, J. S. Electroless Ni−P/Ni−B duplex coatings for improving the hardness and the corrosion resistance of AZ91D magnesium alloy. Appl. Surf. Sci. 2008, 254, 4949−4955. (38) Guo, R. H.; Jiang, S. Q.; Yuen, C. W. M.; Ng, M. C. F. Microstructure and electromagnetic interference shielding effectiveness of electroless Ni−P plated polyester fabric. J. Mater. Sci.: Mater. Electron. 2008, 20, 735−740. (39) Su, Y.; Zhou, B.; Liu, L.; Lian, J.; Li, G. Electromagnetic shielding and corrosion resistance of electroless Ni−P and Ni−P−Cu coatings on polymer/carbon fiber composites. Polym. Compos. 2015, 36, 923−930. (40) Ohring, M. Materials Science of Thin Films, 2nd ed.; Academic Press: London, 2002. (41) Miyajima, T.; Ibusuki, T.; Umehara, S.; Sato, M.; Eguchi, S.; Tsukada, M.; Kataoka, Y. Transmission electron microscopy study on the crystallization and boron distribution of CoFeB/MgO/CoFeB magnetic tunnel junctions with various capping layers. Appl. Phys. Lett. 2009, 94, No. 122501. (42) Keiser, B. E. Principles of Electromagnetic Compatibility; Artech House Inc.: Dedham, MA, 1979; p 341. (43) Zhao, B.; Guo, X. Q.; Zhao, W. Y.; Deng, J. S.; Fan, B. B.; Shao, G.; Bai, Z. Y.; Zhang, R. Facile synthesis of yolk−shell Ni@ void@ SnO2 (Ni3Sn2) ternary composites via galvanic replacement/ Kirkendall effect and their enhanced microwave absorption properties. Nano Res. 2017, 10, 331−343. (44) Zhao, B.; Zhao, C. X.; Li, R. S.; Hamidinejad, S. M.; Park, C. B. Flexible, Ultrathin, and High-Efficiency Electromagnetic Shielding Properties of Poly (Vinylidene fluoride)/Carbon Composite Films. ACS Appl. Mater. Interfaces 2017, 9, 20873−20884. (45) Zhao, B.; Fan, B. B.; Shao, G.; Zhao, W. Y.; Zhang, R. Facile synthesis of novel heterostructure based on SnO2 nanorods grown on submicron Ni walnut with tunable electromagnetic wave absorption capabilities. ACS Appl. Mater. Interfaces 2015, 7, 18815−18823. (46) Zhao, B.; Guo, X. Q.; Zhao, W. Y.; Deng, J. S.; Shao, G.; Fan, B. B.; Bai, Z. Y.; Zhang, R. Yolk−Shell Ni@ SnO2 Composites with a Designable Interspace To Improve the Electromagnetic Wave Absorption Properties. ACS Appl. Mater. Interfaces 2016, 8, 28917− 28925. (47) Kong, J. A. Electromagnetic Wave Theory; John Wiley & Sons, 2000. (48) Sarto, M. S. In A Matrix Surface Impedance Formulation for the Analysis of EM-Interactions to Finite Laminated Composite Slabs, Electromagnetic Compatibility, Symposium Record. IEEE 1996 International Symposium on. IEEE, 1996; pp 168−173. (49) An, B.; Li, Y. J.; Liu, Y.; Wang, Y. G.; Zhang, L. C.; Wang, W. M. Unique corrosion behavior of Fe78Si9B13 glassy alloy with different circumferential speeds under various chloride ion levels. J. Alloys Compd. 2014, 593, 16−23.

42199


NiâCuâP Metallic Glass ... - ACS Publications

Recommend Documents

NiâCuâP Metallic Glass ... - ACS Publications