大丝束PAN纤维热反应特性及其在连续预氧化过程中的结构性能演变

陈肖寒; 郭利闯; 黄翔宇; 王晓旭; 刘杰; 王春华

doi:10.13801/j.cnki.fhclxb.20220225.001

大丝束PAN纤维热反应特性及其在连续预氧化过程中的结构性能演变

doi: 10.13801/j.cnki.fhclxb.20220225.001

1.
北京化工大学常州先进材料研究院　碳纤维工程与技术研究中心，常州 213164
2.
上海石油化工股份有限公司，上海 200540
3.
北京化工大学　材料科学与工程学院，北京 100029

基金项目: 常州市应用基础研究计划(CJ20210029)

详细信息

通讯作者:
王春华，硕士，高级工程师，研究方向为碳纤维、纳米纤维的制备和应用　E-mail: 382755801@qq.com

中图分类号: TQ342.74
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出版历程
- 收稿日期: 2021-12-17
- 修回日期: 2022-01-22
- 录用日期: 2022-02-11
- 网络出版日期: 2022-02-28
- 刊出日期: 2023-01-15

Thermal reaction characteristics of large tow PAN precursors and their evolution of structure and properties during continuous pre-oxidation

1.
Research Center of Carbon Fiber Engineering and Technology, Beijing University of Chemical Technology Changzhou Institute of Advanced Materials, Changzhou 213164, China
2.
Shanghai Petrochemical CO., LTD., Shanghai 200540, China
3.
College of Materials Science and Engineering, Beijing University of Chemical Technology, Beijing 100029, China

Funds: Supported by Changzhou Sci & Tech Program (CJ20210029)

摘要

摘要: 利用热应力、DSC、FTIR、元素分析(EA)、XRD及力学性能、密度等测试表征手段，结合小丝束(24K)聚丙烯腈(PAN)原丝，解析了大丝束(48K) PAN原丝的热反应特性，并采用50 min连续预氧化制备高性能大丝束碳纤维，研究了大丝束PAN原丝连续预氧化过程中的结构性能演变规律。结果表明，大丝束PAN纤维的化学热应力是小丝束的1.13~1.43倍，且启动温度更低，当温度为250℃时，化学热应力差值最大，对应大丝束纤维密度为1.316 g/cm³；纤维内准晶区在反应初期即大量转化为无定形状态，准晶区晶粒尺寸呈现先增大后减小的趋势；50 min连续预氧化制备的大丝束碳纤维单丝拉伸强度和拉伸模量分别为4 240 MPa和244 GPa，相关力学性能达到市售国外大丝束碳纤维同等水平。
- 大丝束 /
- 碳纤维 /
- 预氧化 /
- 热应力 /
- 结构 /
- 性能
Abstract: Thermal stress, DSC, FTIR, element analysis (EA), XRD, mechanical properties and density were used to analyze the thermal reaction characteristics of large tow polyacrylonitrile (PAN) precursors (48K) in combination with small tow PAN precursors (24K). The large tow carbon fibers were prepared by 50 min continuous pre-oxidation method, in which the evolution of structure and properties were studied. The results show that the thermal stress of large tow PAN precursors is 1.13-1.43 times of small tow PAN precursors, and the starting temperature is lower. The difference of thermal stress reaches maximum at 250℃ and the corresponding density of large tow fibers is 1.316 g/cm³. The crystal regions of PAN precursors transform into amorphous regions rapidly at the initial stage of reaction, and the grain size of the crystal regions increases first and then decreases. The monofilament tensile strength and modulus of large tow carbon fibers prepared by 50 min continuous pre-oxidation are 4240 MPa and 244 GPa, respectively, which are at the same level as those commercial foreign large tow carbon fibers.
- large tow /
- carbon fibers /
- pre-oxidation /
- thermal stress /
- structure /
- performance

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图 1 热应力记录装置示意图

Figure 1. Schematic diagram of thermal stress recording device

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图 2 大丝束碳纤维制备示意图

Figure 2. Schematic diagram of large tow carbon fibers manufacturing process

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图 3 (a) 24K-PAN和48K-PAN纤维热应力曲线(升温速率为1℃/min)；(b) 48K-PAN和24K-PAN纤维热应力比值和差值的变化曲线

Figure 3. (a) Thermal stress curves of 24K-PAN and 48K-PAN precursors (Heating rate: 1℃/min); (b) Variable curves of ratio and difference of thermal stress between 48K-PAN and 24K-PAN precursors

τ—Thermal stress; Δτ—Difference of thermal stress

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图 4 24K-PAN小丝束(a)和48K-PAN大丝束(b)纤维样品在空气气氛下的DSC曲线(升温速率5℃/min)

Figure 4. DSC curves of 24K small tow (a) and 48K large tow PAN (b) fiber samples in air atmosphere (Heating rate: 5℃/min )

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图 5 不同温度下24K-PAN和48K-PAN纤维密度对比

Figure 5. Density contrast of 24K-PAN and 48K-PAN precursors at different temperatures

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图 6 48K-PAN纤维预氧化各温区的FTIR图谱

Figure 6. FTIR spectra of pre-oxidation precursors of 48K-PAN fiber at different zones

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图 7 不同温区48K-PAN预氧化纤维的XRD图谱及分峰拟合示意图

Figure 7. XRD patterns of pre-oxidized precursors of 48K-PAN fiber at different zones and peak fitting diagram

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图 8 3种碳纤维的XRD图谱

Figure 8. XRD patterns of three kinds of carbon fiber

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表 1 不同温区预氧化碳纤维编号

Table 1. Sample No. of carbon fiber at different pre-oxidized zones

Temperature/℃	Sample No.
210	P1
225	P2
240	P3
250	P4
260	P5

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表 2 24K聚丙烯腈(PAN)纤维和48K PAN纤维的主要性能

Table 2. Main properties of 24K and 48K polyacrylonitrile (PAN) precursors

Property	24K-PAN	48K-PAN
Diameter/μm	11.83	11.82
Tensile strength/GPa	0.69	0.68
ΔH/(J·g⁻¹)	2523	2531
Crystallinity/%	60.9	61.6
Grain size/nm	9.08	9.08
Note: ∆H—Enthalpy of thermal reaction.

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表 3 不同温度下24K-PAN和48K-PAN纤维DSC参数

Table 3. DSC parameters of 24K-PAN and 48K-PAN fiber at different temperatures

Temperature/℃	T_onset/℃		T_Peak1/℃		T_Peak2/℃		∆H/(J·g⁻¹)
Temperature/℃	24K	48K	24K	48K	24K	48K	24K	48K
80	210	211	271	271	323	323	2523	2531
145	209	212	269	272	322	322	2558	2496
190	209	211	270	270	322	324	2685	2575
215	216	215	267	267	322	323	2246	2231
235	223	223	264	264	323	323	1965	1917
250	229	233	—	—	321	322	1480	1209
275	249	249	—	—	320	319	824	794
Notes: T_onset—Onset temperature of thermal reaction; T_Peak1—First peak temperature of DSC curve; T_Peak2—Second peak temperature of DSC curve.

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表 4 各阶段大丝束PAN预氧化纤维的相对环化度R_CI、脱氢指数R_D、密度和氧含量

Table 4. Relative cyclization index R_CI, relative dehydrogenation index R_D, density and oxygen content of pre-oxidized precursors of large tow PAN fiber at each zone

Sample	R_CI/%	R_D/%	Oxygen content/wt%	Density/(g·cm⁻³)
PAN	22.8	53.5	3.05	1.192
P1	42.3	66.2	3.40	1.205
P2	53.2	102.7	4.44	1.230
P3	65.7	114.8	5.55	1.269
P4	73.8	116.1	8.58	1.323
P5	79.1	116.8	11.05	1.372

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表 5 不同温区48K-PAN预氧化纤维的晶态参数

Table 5. Crystalline parameters of pre-oxidized precursors of 48K-PAN fiber at different zones

Sample	2θ/(°)	L₍₁₀₀₎/nm	X_c/%
PAN	16.78	9.08	56.6
P1	16.90	11.98	25.3
P2	16.88	11.06	21.7
P3	16.78	8.39	18.0
P4	16.81	4.42	5.6
P5	—	—	—
Notes: L₍₁₀₀₎—Microcrystal size perpendicular to (100) (2θ=16.7°); X_c—Degree of crystallinity.

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表 6 3种大丝束碳纤维的力学性能和结构参数

Table 6. Mechanical properties and structural parameters of three kinds of large tow carbon fibers

Performance	Zoltek-50K	SGL-50K	Domestic- 50 min
Density/(g·cm⁻³)	1.810	1.800	1.791
Tensile strength/MPa	4137	4000	4240
Tensile modulus/GPa	242	240	244
d₍₀₀₂₎/nm	0.352	0.354	0.355
L_c/nm	2.02	1.73	1.68
V_p/%	16.2	16.2	16.3
Notes: d₍₀₀₂₎—(002) crystal plane spacing of carbon fiber; L_c—Crystallite size of carbon fiber; V_p—Porosity of carbon fiber.

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