萘系中间相沥青分子结构对其炭纤维性能的影响

XU Hui-tao; GUO Jian-guang; LI Wen-long; LI Xuan-ke

doi:10.1016/S1872-5805(23)60709-7

萘系中间相沥青分子结构对其炭纤维性能的影响

doi: 10.1016/S1872-5805(23)60709-7

徐辉涛^1,,
郭建光¹,
李文龙¹,
李轩科^{1, 2, ,}

1.
湖南大学材料科学与工程学院，先进炭材料及应用技术湖南省重点实验室，湖南长沙 410082
2.
武汉科技大学化学与化工学院，湖北武汉 430080

基金项目: 国家自然科学基金(U1864207)

详细信息

通讯作者:
李轩科，博士，教授. E-mail：xkli8524@sina.com

中图分类号: TQ342⁺74
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出版历程
- 收稿日期: 2020-02-09
- 修回日期: 2022-10-18
- 网络出版日期: 2022-11-03
- 刊出日期: 2023-04-07

The effect of the molecular structure of naphthalene-based mesophase pitch on the properties of carbon fibers derived from it

1.
College of Materials Science and Engineering, Hunan Province Key Laboratory for Advanced Carbon Materials and Applied Technology, Hunan University, Changsha 410082, China
2.
School of Chemistry and Chemical Engineering, Wuhan University of Science and Technology, Wuhan 430080, China

Funds: National Natural Science Foundation of China (U1864207)

More Information

Author Bio:
徐辉涛，硕士研究生. E-mail：HuitaoXu1995@163.com

Corresponding author: LI Xuan-ke, Ph. D. Professor. E-mail: xkli8524@sina.com

摘要

摘要: 中间相沥青基炭纤维因具有高模量、低电阻率、高导热等特性，在许多领域有广阔的应用前景。本文分别以采用HF/BF₃催化萘一步法制备的中间相沥青（AR-MP）和采用AlCl₃催化萘两步法制备的中间相沥青（N-MP）为原料，制备了高性能炭纤维。通过元素分析、TG-MS、FT-IR、¹³C-NMR、MALDI-TOF-MS、XRD和SEM等手段对上述沥青和纤维进行了分析表征，对比了不同催化聚合工艺制备的中间相沥青的分子结构和性能，并进一步探究了中间相沥青分子结构差异对其炭纤维结构和性能的影响。结果表明：AR-MP分子构型偏向于半刚性的棒状，含有更多的环烷结构和甲基侧链，其预氧化后的纤维显示出更好的碳平面取向，使其石墨化纤维具有更好的热导率(716 W/m·K)；而N-MP分子构型偏向于刚性的圆盘状、芳香度高，其纤维在后续热处理过程中产生的缺陷更少，石墨化后具有更大的拉伸强度(3.47 GPa)。
- 萘沥青 /
- 中间相沥青 /
- 催化聚合法 /
- 分子结构 /
- 微晶尺寸
Abstract: Mesophase pitch-based carbon fibers (MPCFs) have a high modulus of elasticity, low electrical resistivity and high thermal conductivity, so can be used in many fields. Carbon fibers were prepared from two naphthalene-based mesophase pitches, one synthesized by a HF/BF₃ catalytic one-step method (AR-MP) and the other by an AlCl₃ catalytic two-step method (N-MP). The mesophase pitches, spun pitch fibers, pre-oxidized fibers, carbonized fibers and graphitized fibers produced from them were characterized by TG-MS, FT-IR, ¹³C-NMR, MALDI-TOF-MS, XRD, SEM and elemental analysis. The molecular structures and properties of mesophase pitches were compared, and the effects of molecular structures on the structures and properties of the carbon fibers produced from them were measured. In comparison to N-MP, AR-MP has a rod-like semi-rigid molecular configuration containing more naphthenic structures and methyl side chains. The pre-oxidized fibers derived from AR-MP have a better carbon layer orientation, so that their graphitized fibers have a higher thermal conductivity of 716 W/(m·K). N-MP has a higher aromaticity with a disc-like rigid molecular configuration, so that the graphitized fibers prepared from it have a higher tensile strength of 3.47 GPa due to fewer defects being formed during preparation. The molecular structures of AR-MP and N-MP have an obvious influence on the structures and properties of their graphitized fibers.
- Naphthalene-based pitch /
- Mesophase pitch /
- Catalytic polycondensation /
- Molecular structure /
- Crystalline size

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FIG. 2240. FIG. 2240.

FIG. 2240.. FIG. 2240.

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Figure 1. Typical optical micrographs of (a) AR-MP and (b) N-MP

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Figure 2. FT-IR spectra of AR-MP and N-MP

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Figure 3. Solid ¹³C-NMR spectra of AR-MP and N-MP

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Figure 4. MALDI-TOF-MS spectra of AR-MP and N-MP

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Figure 5. (a) TG and (b) DSC curves of AR-MP and N-MP under inert atmosphere

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Figure 6. (a) TG and (b) DSC curves of AR-PFs and N-PFs under air atmosphere

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Figure 7. XRD patterns of mesophase pitches, spun pitch fibers, pre-oxidized fibers and carbonized fibers

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Figure 8. (a) d₀₀₂ and (b) Lc values of spun pitch fibers, pre-oxidized fibers, carbonized fibers and graphitized fibers

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Figure 9. SEM images of (a, c) AR-GFs and (b, d) N-GFs

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Table 1. General properties of AR-MP and N-MP

Sample	SP (°C)	TS^a	QI	Elemental analysis (wt%)				n(H)/n(C)	Ash content	Spinning viscosity (Pa·s)
Sample	SP (°C)	TS^a	QI	C	H	N	S	n(H)/n(C)	Ash content	Spinning viscosity (Pa·s)
AR-MP	234	42.9%	26.7%	95.1	4.80	0	0.05	0.60	2×10⁻⁵	22
N-MP	240	37.2%	32.6%	95.8	4.12	0	0.04	0.52	5×10⁻⁵	37
Note: SP—softening point, TS^a—toluene soluble, QI—quinoline insoluble

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Table 2. Aromatic carbon and Aliphatic carbon content of AR-MP and N-MP

Sample	Aliphatic (%)			Aromatic (%)				C_ar3/C_ar2	fa
Sample	C_chain	CH₂	CH₃	CH_ar	C_ar3	C_ar2	C_ar^s	C_ar3/C_ar2	fa
AR-MP	10.06	11.28	5.79	4.88	40.38	16.77	10.84	2.41	0.73
N-MP	4.51	4.10	3.69	6.15	54.51	15.16	11.89	3.59	0.88
Note: C_chain—bridge/hydroaromatic structures (methylene carbons to two aromatic rings); CH₂—all the rest of methylene carbons; CH₃—methyl carbons; CH_ar—protonated aromatic carbons; C_ar3—peri-condensed aromatic carbons; C_ar2—cata-condensed aromatic carbons; C_ar^s—aromatic carbons joined to aliphatic chains; fa—aromaticity

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Table 3. The X-ray parameters of mesophase pitches and spun pitch fibers

Sample	d₀₀₂ (nm)	FWHM (°)	Lc (nm)	N
AR-MP	0.3520	3.080	2.93	9
N-MP	0.3410	4.606	1.96	6
AR-PFs	0.3517	2.848	3.17	10
N-PFs	0.3488	4.637	1.95	6

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Table 4. The properties and X-ray parameters of AR-GFs and N-GFs

Sample	Properties				Crystal parameters
Sample	TS^b (GPa)	TM (GPa)	ρ (μΩ·m)	TC (W/(m·K))	d₀₀₂ (nm)	La (nm)	Lc (nm)
AR-GFs	3.02±0.78	634±75	1.77	716±43	0.3369	60.12	30.36
N-GFs	3.47±0.48	652±70	1.82	704±45	0.3370	62.09	29.03
Note: TS^b—tensile strength; ρ—resistivity; TM—tensile modulus; TC—thermal conductivity; DC—dispersion coefficient

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