Tao Huangabc,
Xiaoliang Zengbd,
Yimin Yaobd,
Rong Sun*b,
Fanling Meng*a,
Jianbin Xue and
Chingping Wongf
aDepartment of Materials Science and Key Lab of Automobile Materials of MOE, Jilin University, Changchun 130012, China. E-mail: mfl@jlu.edu.cn; Tel: +86-431-85168444
bShenzhen Institutes of Advanced Technology, Chinese Academy of Sciences, Shenzhen 518055, China. E-mail: rong.sun@siat.ac.cn; Tel: +86-755-86392158
cCollege of Information and Technology, Jilin Normal University, China
dShenzhen College of Advanced Technology, University of Chinese Academy of Sciences, China
eDepartment of Electronics Engineering, The Chinese University of Hong Kong, Hong Kong, China
fSchool of Materials Science and Engineering, Georgia Institute of Technology, Atlanta, GA 30332, USA
First published on 24th March 2016
Polymer-based materials have widely been used for electronics packaging owing to their excellent physical and chemical properties. However, polymer materials usually have low thermal conductivity, which thus may impair the performance and reliability of modern electronics. In this paper, we report an epoxy-based composite with increased thermal conductivity by using graphene oxide-encapsulated boron nitride (h-BN@GO) hybrids as fillers. The thermal conductivity of the obtained composites increased with the loading of h-BN@GO hybrids to a maximum of 2.23 W m−1 K−1 when the loading of h-BN@GO hybrids was 40 wt%, which is double that of composites filled with h-BN. This increase is attributed to the presence of GO, which improved the compatibility of h-BN with epoxy resin, along with the reduced interfacial thermal resistance between h-BN and epoxy resin. In addition, the effects of h-BN@GO hybrids on the thermal and dielectric properties of epoxy composites were also investigated. The prepared h-BN@GO/epoxy composites exhibit outstanding performance in dimensional stability, slightly reduced thermal stability, and enhanced dielectric properties, which make them suitable as excellent electronics packaging materials.
Conventionally, the introduction of thermally conductive fillers into polymers is a common method of increasing the thermal conductivity of polymer-based materials, which is due mainly to it being an easy process and having the potential for large-scale production. Various low-cost ceramic fillers, including alumina (Al2O3),2 silicon nitride (Si3N4),3 aluminium nitride (AlN),4,5 and silicon carbide (SiC),6 etc., have widely been used as thermally conductive fillers. However, the obtained polymer composites still have a low thermal conductivity of below 2.0 W m−1 K−1. In recent years, carbon nanotubes1,7–9 and graphene10–15 have also been applied as fillers to fabricate polymer composites with high thermal conductivity, owing to their intrinsic extremely high thermal conductivity. For example, theoretical simulations and experimental results demonstrate that the thermal conductivity of graphene is as high as 6000 W m−1 K−1 (ref. 16). However, the high electrical conductivity of these carbon-based materials limits their applications in the electronics packaging field, in which electrical insulation is required. Among thermally conductive fillers, hexagonal boron nitride (h-BN), which has a similar hexagonal structure to graphite, has attracted far more interest because of its unique advantages.17–22 For example, in contrast to graphite, h-BN has a wider band gap, lower density and higher thermal conductivity compared with the aforementioned ceramic fillers. Therefore, h-BN has great potential to achieve high thermal conductivity in polymer-based materials.23 In fact, the increase in thermal conductivity by using h-BN is usually limited, owing to high interfacial thermal resistance between h-BN and polymer matrices.24 In order to minimize interfacial thermal resistance, lots of effort has been devoted to the functionalization of h-BN.25–27 However, the increase in thermal conductivity is still insufficient, because the functionalization of h-BN usually compromises the intrinsic thermal conductivity of h-BN. Therefore, it is desirable to develop a facile and eco-friendly strategy for functionalizing h-BN.
In this work, we fabricated a novel thermally conductive h-BN@GO hybrid by an electrostatic self-assembly strategy. Epoxy-based composites using this hybrid as a filler were then fabricated. It was found that the thermal conductivity of the obtained composites increased with the loading of h-BN@GO hybrids and reached a maximum of 2.23 W m−1 K−1 when the loading of h-BN@GO hybrids was 40 wt%, which is double that of composites filled with h-BN. This increase can be attributed to the presence of GO, which improves the compatibility of h-BN with epoxy resin, along with the reduced interfacial thermal resistance between h-BN and epoxy resin. Furthermore, the prepared h-BN@GO/epoxy composites exhibited excellent performance in dimensional stability and thermal conductivity, together with dielectric properties, and retained thermal stability for electronics packaging applications.
K = −QL/AΔT | (1) |
The h-BN@GO hybrids were prepared via electrostatic self-assembly between h-BN and GO, and the mechanism is illustrated in Fig. 3. It is well known that GO can disperse well in water owing to the presence of hydrophilic groups such as carboxyl, carbonyl, and hydroxyl groups. As for hydrophobic h-BN, functionalization by APTES also allows it to disperse well in water, which is due to the introduction of hydrophilic amino and hydroxyl groups on its surface, as shown in Fig. 3. When the solution of GO and h-BN was mixed, all the fillers quickly settled to the bottom forming brown h-BN@GO hybrids, as shown in Fig. 3. This is a clear indication of self-assembly between GO and h-BN particles. Functionalization of h-BN particles leads to a change in their surface charge from neutral to positive, and thus h-BN has the ability to attract negatively charged GO sheets in water.24,28 In addition, the whole assembly process is so easy and quick that the h-BN@GO hybrids can be fabricated on a large scale.
Fig. 4 shows the XRD patterns of h-BN, GO and h-BN@GO hybrids. Pristine h-BN exhibits a well-crystallized structure. The distinct characteristic peaks at 26.6°, 41.6°, 43.8°, 50.1°, 55.0°, 75.9°, and 82.1° correspond to the (002), (100), (101), (102), (004), (110) and (112) lattice planes, respectively. Besides the characteristic peaks of h-BN, the h-BN@GO hybrids exhibit one distinct peak at 11.4°, which is similar to that of GO and demonstrates the successful preparation of h-BN@GO hybrids.
TGA curves provide further evidence of the successful self-assembly of h-BN with GO, and the GO content in the h-BN@GO hybrids can be determined. Fig. 5 shows the TGA curves of GO, h-BN and h-BN@GO hybrids in air. Pristine h-BN exhibited high thermal stability up to 900 °C without any decomposition, which is consistent with a previous report.29 In contrast, pristine GO displayed poor thermal stability and thermally decomposed completely at 600 °C. As for h-BN@GO hybrids, there was approximately zero mass loss at temperatures below 260 °C and only 5 wt% mass loss when the temperature reached 900 °C, which suggests that the GO content in h-BN@GO is approximately 5 wt%.
The surface morphologies of h-BN@GO hybrids together with that of pristine h-BN were investigated by SEM and TEM. Fig. 6a shows that pristine h-BN microplatelets with an average lateral size of about 2 μm exhibit a highly flaked structure and smooth surface. However, after electrostatic self-assembly h-BN was decorated with ultrathin GO nanosheets, which show clear creases and rough textures on the h-BN surface (Fig. 6b). The wrinkles of GO on the h-BN surface are further confirmed by the TEM images, in which flexible, ultrathin GO sheets have successfully stuck to the h-BN particles. The tighter wrapping morphology of GO on the h-BN surface allows the removal of absorbed water and air from h-BN, which will improve the interaction with h-BN.
Fig. 6 SEM images of (a) raw h-BN and (b) h-BN@GO hybrids; (c) and (d) TEM images of h-BN@GO hybrids. |
The surface chemical composition of h-BN@GO was further characterized by FTIR spectroscopy, as shown in Fig. 7. h-BN exhibits a strong characteristic in-plane B–N stretching vibration at 1367 cm−1 and an out-of-plane bending vibration at 810 cm−1 respectively.30–32 After the amination reaction of h-BN, several minor bands at around 2982 cm−1, which correspond to C–H stretching vibrations of the hydrocarbon chains of the grafting APTES, are observed.32 In the spectrum of GO, the peaks located at 3422 and 1631 cm−1 correspond to –OH and –CC groups, respectively. As for the h-BN@GO spectrum, the characteristic peaks of h-BN and GO are all observed, which reveals that GO has stuck to the surface of h-BN. Note that the presence of abundant hydroxyl and carboxyl groups on h-BN@GO will facilitate the chemical interactions of h-BN@GO with polymer matrices.
Fig. 8 Thermal conductivity of (a) GO/epoxy composites and (b) h-BN@GO/epoxy and h-BN/epoxy composites with different mass fractions. |
To confirm the aforementioned deduction, the interfacial thermal resistance between h-BN@GO and the epoxy matrix was estimated according to previous theoretical models.33 The Maxwell-Garnett effective medium approximation (EMA) has commonly been used to calculate interfacial thermal resistance.34 Unfortunately, it is not able to fit our data, because it is based on the assumption that the fillers are completely surrounded by the matrix. Therefore, the nonlinear model proposed by Foygel et al. should be suitable for our h-BN@GO/epoxy composites. The Foygel model can be described as:33
K = k0〈Vf − VC(β)t(β)〉 | (2) |
VC = 0.62/β | (3) |
R0 = (k0LVCt(β))−1 | (4) |
Based on the experimental results, we can obtain a value of VC of 0.02. By fitting the experimental values of thermal conductivity using eqn (2), we can obtain values of the parameters k0 and t(β), as shown in Fig. 9. The best fit gives values of k0 for h-BN/epoxy composites and h-BN@GO/epoxy composites of 8 W m−1 K−1 and 30 W m−1 K−1, respectively. We also note that the exponent t(β) for h-BN and h-BN@GO was found to be 1.5 and 1.7, respectively, which is the signature of a three-dimensional (3D) transport process. According to eqn (2), k0 is the expected contribution of the thermally conductive filler network alone. Obviously, the value of k0 of h-BN@GO/epoxy composites is much higher than that of h-BN/epoxy composites and is comparable to that of a single-walled carbon nanotube network in poly(methyl methacrylate) (PMMA) composites. It is 100 times higher than the thermal conductivity of epoxy resin. However, it is still much lower than the value of 260 W m−1 K−1 of pure h-BN, which indicates that the thermally conductive network constructed from h-BN@GO has deteriorated due to interfacial thermal resistance. Using the obtained values of the parameters k0 and t(β), the values of R0 for h-BN/epoxy and h-BN@GO/epoxy resin composites are 4.10 × 108 K W−1 and 2.37 × 108 K W−1, respectively. Obviously, the interfacial thermal resistance of h-BN@GO/epoxy composites is lower than that of h-BN/epoxy composites, which confirms our deduction that GO can not only be used as a bridge between h-BN but also improves the compatibility between h-BN and epoxy resins.
Fig. 9 Comparison between the simulated thermal conductivity based on the Foygel model and the experimental values. |
A thermal percolation phenomenon has not been explicitly explained. Some studies have demonstrated thermal percolation behavior in carbon-based composites,36 whereas others have shown continuous linear dependence.37 In our work, we believe that the loading of the matrix with h-BN@GO, which increased the thermal conductivity, is characterized by a percolation threshold. The conductivity of a polymer composite in the vicinity of the percolation threshold is described by eqn (2). Using Foygel's results and the diameter and length of our h-BN@GO particles, we estimate the value of VC = 0.02. The best fit to eqn (2) with k0 and t(β) as fitting parameters provides values of k0 = 30 W m−1 K−1 and t(β) = 1.7 for h-BN@GO/epoxy composites. The fit follows all of the experimental data points, which suggests that the thermal conductivity relies on a percolation network of h-BN@GO, rather than isolated filler particles. Below the percolation threshold (Vf < 2 vol%), h-BN@GO particles are not sufficiently in contact, which causes phonon scattering, and the thermal conductivity is below 0.62 W m−1 K−1. Above the thermal conductivity percolation threshold (Vf > 2 vol%), the rise in the thermal conductivity indicates that a conducting network with an increased number of direct h-BN@GO–h-BN@GO contacts and a decreased number of polymer-mediated boundaries has been formed. Therefore, heat is effectively transported through the percolation network.
Thermal stability is one of the most important properties of the composites, because it influences the processing and service life performance of the composites. The TGA curves of pure epoxy resin and h-BN@GO/epoxy composites with different loadings of h-BN@GO are shown in Fig. 10. The composites remained stable up to 300 °C and then completely decomposed at above 600 °C, leaving different residues for different h-BN@GO loadings. It was found that Td5%, which is an indication of thermal stability, increased with the addition of h-BN@GO. In detail, Td5% gradually increased from 298 °C for pure epoxy resin to 335 °C for the composite containing 40 wt% h-BN@GO. This is mainly attributed to stabilization by h-BN, which almost does not decompose below 1000 °C.38
Fig. 11 shows the dependence on frequency of the dielectric permittivity and loss for pure epoxy resin and h-BN@GO/epoxy composites. The dielectric permittivity of the composites was found to decrease as the frequency changed from 1 kHz to 10 MHz (Fig. 11a), owing to the orientation of the dipoles in the polymer chains. Owing to the comparatively high dielectric permittivity of h-BN and GO, the addition of the h-BN@GO composites resulted in a modest increase in dielectric permittivity. For example, the dielectric permittivity increased from 6.8 for pure epoxy resin to 12.5 for the 20 wt% h-BN@GO/epoxy composite. The dielectric loss of the h-BN@GO/epoxy composites with different fillers also decreased with an increase in frequency in the range of 1 kHz to 10 MHz (Fig. 11b). Furthermore, the addition of h-BN@GO led to an increase in dielectric loss at low frequency from 103 Hz to 105 Hz, and the dielectric loss was independent of the h-BN@GO loading. At high frequency, the effect of h-BN@GO on the dielectric loss was negligible, which is attributed to the presence of GO. As proved by a previous study,39 the addition of GO to polymer composites will lead to an increase in dielectric loss owing to interfacial polarization at frequencies of below 104 Hz. Despite the increase in dielectric loss, it still remained lower than 0.05 at frequencies of above 106 Hz. Therefore, the h-BN@GO/epoxy composites with high thermal conductivity and an increased dielectric constant are suitable for applications in semiconductor devices packaging, in which both high thermal conductivity and an increased dielectric constant are required.
Fig. 11 Dependence of (a) the dielectric permittivity and (b) the dielectric loss of h-BN@GO/epoxy composites on the frequency. |
Dimensional stability is a key property of polymer composites, because a mismatch in dimensional stability between two different materials will lead to deformation of the products. The coefficient of thermal expansion is an indication of the dimensional stability of the composites and can be determined by thermomechanical analysis (TMA) within the temperature range from 25 to 200 °C, as shown in Fig. 12a. The values of CTE in the glassy region and rubbery region,40,41 which are marked CTE1 and CTE2, were determined by the slope of a linear regression plot in the temperature intervals of 40–100 °C and 180–300 °C, respectively, based on eqn (5):
(5) |
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