Interfacial properties of carbon nanotubes/rubber composites: Effects of specific surface area of carbon nanotubes
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摘要: 橡胶大分子和无机纳米填料由于相互作用形成的界面是决定弹性体复合材料性能的重要因素。利用原子力显微镜的峰值力定量纳米力学映射模式(AFM-QNM)建立了碳纳米管/溶聚丁苯橡胶(CNT/SSBR)复合材料的界面纳米力学性能和界面厚度的定量表征方法，研究揭示了CNT的比表面积对CNT/SSBR复合材料的界面纳米力学性能和界面厚度的影响。结果表明，随着CNT的比表面积的增大，CNT/SSBR复合材料的界面纳米力学性能逐渐增强，界面厚度逐渐增大，这是由于CNT表面作用的橡胶大分子不动链数增加。Abstract: The interface between rubber macromolecules and inorganic nano-filler is an important factor to determine the properties of elastomer composites. The peak force quantitative nanomechanical mapping mode of atomic force microscopy (AFM-QNM) was attempted to quantify the interfacial nanomechanical properties and interfacial thickness of carbon nanotubes/Soluble styrene butadiene rubber (CNT/SSBR) composites, and reveal the effects of the specific surface area of the CNT on the interfacial nanomechanical properties and interfacial thickness of CNT/SSBR composites. The results show that with the increase of specific surface area of CNT, both the interfacial nanomechanical properties and interfacial thickness of CNT/SSBR composites gradually increase, which is due to the increase in the number of immobile rubber macromolecules chains acting on the CNT surface.
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Key words:
- carbon nanotubes /
- rubber composites /
- atomic force microscopy /
- nanomechanics /
- specific surface area
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图 1 CNT-40、CNT-110和CNT-350的FTIR图谱
Figure 1. FTIR spectra of CNT-40, CNT-110 and CNT-350
图 2 CNT-40、CNT-110和CNT-350的拉曼光图谱
Figure 2. Raman spectra of CNT-40, CNT-110 and CNT-350
ID—Intensity of the D peak; IG—Intensity of the G peak; ID/IG—Intensity ratio of peak D to peak G
图 3 CNT-350/溶聚丁苯橡胶(SSBR)复合材料的原子力显微镜(AFM)图像(扫描尺寸为3 μm)
Figure 3. Atomic force microscopy (AFM) images of CNT-350/solution polymerized butadiene styrene rubber (SSBR) composites (Scan size is 3 μm) ((a) Height image; (b) Modulus image; (c) Adhesion image)
图 4 CNT-350/SSBR复合材料的AFM图像(扫描尺寸为1 μm)
Figure 4. AFM images of CNT-350/Soluble styrene butadiene rubber (SSBR) composites (Scan size is 1 μm) ((a) Height image; (b) Modulus image; (c) Adhesion image)
图 5 基于填料相对于样品表面的位置选择合适的CNT
Figure 5. Schematic representation of the location of filler relative to the sample surface for selecting appropriate CNT (((a),(a’)) Appropriate CNT; ((b),(b’)) Inappropriate CNT)
图 6 CNT-350/SSBR复合材料的界面区域的模量-位移曲线
Figure 6. Modulus-displacement curve of the interface region in CNT-350/SSBR composites
图 8 “划线法”统计CNT-350/SSBR复合材料的界面厚度
Figure 8. “Line method” to calculate interfacial thickness of CNT-350/SSBR composites
图 10 CNT/SSBR复合材料的界面区域的模量-位移曲线
Figure 10. Modulus-displacement curves of the interface region in CNT/SSBR composites
图 11 CNT-40/SSBR复合材料每个区域特征点处的AFM力-形变曲线和JKR模拟(对应图10(a)中圆圈标出的a、b、c三点)
Figure 11. AFM unloading force-deformation curves and the JKR simulations at typical points (see circles in Fig. 10(a) a, b, c) in each region of CNT-40/SSBR composites
图 12 CNT-110/SSBR复合材料每个区域特征点处的AFM力-形变曲线和JKR模拟(对应图10(b)中圆圈标出的a、b、c三点)
Figure 12. AFM unloading force-deformation curves and the JKR simulations at typical points (see circles in Fig. 10(b) a, b, c) in each region of CNT-110/SSBR composites
图 13 不同CNT/SSBR复合材料的杨氏模量统计
Figure 13. Young’s modulus of different CNT/SSBR composites
图 14 不同CNT/SSBR复合材料的界面厚度统计
Figure 14. Interfacial thickness of different CNT/SSBR composites
图 15 SSBR基体和不同CNT/SSBR复合材料的DSC曲线
Figure 15. DSC curves of SSBR and different CNT/SSBR composites
图 16 CNT表面吸附的橡胶大分子链的三种存在形式
Figure 16. Adsorbed chains attached on the CNT surface in three types of topologies
表 1 碳纳米管(CNT)的基本参数
Table 1. Main parameters of carbon nanotube (CNT)
Sample L/μm OD /nm P/% SSA/(m2·g−1) CNT-350 10-30 <8 98 350 CNT-110 10-30 20-30 98 110 CNT-40 10-30 >50 98 40 Notes: L—Length of CNT; OD —Outside diameter of CNT; P—Purity of CNT; SSA—Specific surface area of CNT. 
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表 2 SSBR基体和不同CNT/SSBR复合材料的动力学参数
Table 2. Dynamic mechanical behaviors of SSBR and different CNT/SSBR composites
Sample SSBR CNT-40/SSBR CNT-110/SSBR CNT-350/SSBR Tg/℃ −14.0 −10.9 −10.2 −11.4 ∆Tg/℃ − 3.1 3.8 2.6 ∆Cp/(J·g-1·K−1) 0.12 0.11 0.10 0.09 ∆Cpn/(J·g-1·K−1) 0.12 0.11 0.10 0.09 χim/wt% − 8.3 16.7 25.0 Notes: Tg—Glass transition temperature; ∆Tg—Change in glass transition temperature between pure SSBR and CNT/SSBR composites; ΔCp—Change in heat capacity of the composites at the glass transition temperature; ΔCpn—Normalized change in heat capacity; χim—Mass fraction of immobile rubber macromolecules chains in composites.
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