Improving the mechanical properties and thermal conductivity of mesophase-pitch-based carbon fibers by controlling the temperature in industrial spinning equipment
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摘要: 基于工程化设备，在恒定挤出量条件下，通过调控纺丝温度制备了中间相沥青炭纤维( MPCFs )，探究纺丝温度对MPCFs微观结构、力学和导热性能的影响。结果表明：随着纺丝温度由309升高至320 °C，MPCFs的微观结构由石墨片层细小的褶皱劈裂辐射状结构逐步向石墨片层粗大的劈裂辐射状结构转变，拉伸强度由2.16增大到3.23 GPa，热导率由704升高到1078 W·m−1·K−1。这主要是因为纺丝温度越高，沥青熔体黏度越小，喷丝口处挤出胀大效应越弱，沥青熔体在喷丝孔流道内形成的微晶取向得以保持，以此制备的炭纤维具有更大的晶体尺寸和更高的微晶取向。Abstract: Mesophase-pitch-based carbon fibers (MPCFs) were prepared using industrial equipment with a constant extrusion rate of pitch while controlling the spinning temperature. The influence of spinning temperature on their microstructures, mechanical properties and thermal conductivities was investigated. SEM images of the fractured surface of MPCFs show that the graphite layers have a radiating structure at all spinning temperatures, but change from the fine-and-folded to the large-and-flat morphology when increasing the spinning temperature from 309 to 320 oC . At the same time the thermal conductivity and tensile strength of the MPCFs respectively increase from 704 W·m−1·K−1 and 2.16 GPa at 309 oC to 1 078 W·m−1·K−1 and 3.23 GPa at 320 oC. The lower viscosity and the weaker die-swell effect of mesophase pitch at the outlets of the spinnerets at the higher spinning temperature contribute to the improved orientation of mesophase pitch molecules in the pitch fibers, which improves the crystallite size and orientation of the MPCFs.
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Key words:
- Mesophase pitch /
- Spinning temperature /
- Carbon fiber /
- High thermal conductivity /
- Mechanical properties
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Figure 2. Rheological properties of mesophase pitch: (a) viscosity-temperature curve, (b) variation curves of storage modulus (G'), loss modulus (G''), and loss coefficient (tanδ) with temperature, (c) thermal decomposition behavior and (d) polarized microscope images
Figure 3. XRD patterns of samples with (a) the equatorial scan of MPFs, (b) the meridian scan of MPFs, (c) the azimuthal scan on (002) crystal face of MPFs, (d) the equatorial scan of MPCFs, (e) the meridional scan of MPCFs and (f) the azimuthal scan on the (002) crystal face of MPCFs
Figure 5. SEM images of the cross section of fibers: (a) MPCF-309, (b) MPCF-310, (c) MPCF-311, (d) MPCF-313, (e) MPCF-314, (f) MPCF-316, (g) MPCF-318 and (h) MPCF- 321
Figure 6. Relationship of thermal conductivity and tensile strength to spinning temperature
Figure 7. Microstructural formation mechanism of MPCFs at different spinning temperatures: (a) low spinning temperature, (b) medium spinning temperature and (c) high spinning temperature
Table 1. The basic properties of mesophase pitch
SP/°C TI/% QI/% Ash content/0.1×10−6 Coking value/% H/C AC/% 286.4 75.8 52.6 19.1 90.7 0.54 100 Note: SP, softening point. TI, toluene insoluble. QI, quinoline insoluble. H/C, mole ratio of hydrogen to carbon atoms. AC, anisotropic content. 
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Table 2. Crystalline parameters of MPFs and MPCFs
Samples d002/nm Lc/nm La/nm Z/(°) MPF-309 0.3433 2.22 0.50 40.64 MPF-310 0.3431 2.25 0.48 39.01 MPF-311 0.3428 2.32 0.52 34.85 MPF-312.5 0.3427 2.50 1.64 35.81 MPF-314 0.3426 2.49 1.84 31.56 MPF-316 0.3424 2.54 1.89 30.18 MPF-318 0.3424 2.59 1.88 29.56 MPF-320.5 0.3423 2.66 1.92 28.71 MPCF-309 0.3406 10.76 17.07 14.42 MPCF-310 0.3409 10.89 22.84 14.23 MPCF-311 0.3404 10.98 22.97 12.58 MPCF-312.5 0.3381 10.99 23.87 11.57 MPCF-314 0.3393 11.47 26.17 11.02 MPCF-316 0.3406 11.53 27.14 10.41 MPCF-318 0.3399 12.08 27.50 9.94 MPCF-320.5 0.3366 13.78 27.73 8.48
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Table 3. Microstructure, tensile strength and thermal conductivity of fibers prepared in other studies
Samples Microstructure Tensile strength/GPa Thermal conductivity/(W·m−1·K−1) References Ribbon 3000 °C Ribbon 2.53 ~1150 [26] CM-260 Ribbon / 837 [27] SGF Round 1.07 ± 0.30 / [8] Modified Fiber CB Round / 500 [11] MPCF-3 Round 2.12 1322 [28] XN-90 Round 3.43 500 [29-30] K13C2U Round 3.80 620 [31] K13D2U Round 3.70 800 [32] P120 Split 2.41 640 [29- 33] K1100 Split 3.10 1100 [33, 34] MPCF-320.5 Split 3.23 1077 This work
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