Preparation and performance of highly conductive polypyrrole-modified basalt fiber
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摘要: 玄武岩纤维(BF)具有优异的力学性能、耐腐蚀性和热稳定性，已经广泛使用于国民经济的众多领域。然而由于玄武岩纤维绝缘性，限制了其在电磁屏蔽、静电防护等领域的应用。本研究开发了一种制备导电玄武岩纤维的方法，该方法在实现玄武岩纤维高导电性的同时，提升了玄武岩纤维的拉伸强度，是一种高效、低成本、友好的制备方法。该方法以吡咯单体(Py)、氧化剂氯化铁(FeCl3)和掺杂剂5-磺基水杨酸钠(NaSSA)为原料，通过原位聚合法在玄武岩纤维表面沉积导电聚合物聚吡咯(PPy)，设置不同Py，FeCl3和NaSSA浓度作为参数研究其对玄武岩纤维导电性的影响。在改性过程中，玄武岩纤维表面逐渐由黄褐色变成黑色，表面附着上了均匀厚实的聚吡咯涂层。聚吡咯颗粒展现出较高的掺杂水平、双极化子比例和共轭链长度，说明聚吡咯具有良好的结构。在导电性能方面，PPy改性玄武岩纤维的电阻率最低下降至8 × 10−3 Ω·cm，说明改性后的玄武岩纤维具有优异的导电性。在拉伸性能上，纤维的单丝拉伸强度提升20.6%，并通过差异性分析和Weibull分布模型进行验证，这体现了该方法在实现导电性能的同时保护了纤维结构和力学性能。本研究为扩宽玄武岩纤维的应用领域，及实现功能化玄武岩纤维复合材料提供了一种新的方案。Abstract: Basalt fibers (BF) possess outstanding mechanical properties, corrosion resistance, and thermal stability, making them widely utilized in various sectors of the national economy. However, due to the insulating nature of basalt fibers, their application in areas such as electromagnetic shielding and electrostatic protection is limited. The investigation introduces a method for preparing conductive basalt fibers, which not only enhances the conductivity of basalt fibers but also improves the tensile strength. It is an efficient, low-cost, and environmentally friendly preparation method. The method utilizes pyrrole monomers (Py), iron chloride oxidant (FeCl3), and the dopant sodium 5-sulfosalicylate (NaSSA) as raw materials. Conductive polypyrrole (PPy) is deposited on the surface of basalt fibers through in-situ polymerization. Different concentrations of Py, FeCl3, and NaSSA are investigated as parameters to study their effects on the conductivity of basalt fibers. Through the in-situ polymerization method, basalt fibers gradually change from brown to black, with a uniform, stable, and thick polypyrrole coating on the surface. The polypyrrole particles exhibit a high doping level, bipolaron ratio, and conjugated chain length, indicating a well-defined structure. In terms of electrical conductivity, the resistance of polypyrrole-modified basalt fibers decreases to a minimum of 8 × 10−3 Ω·cm, demonstrating excellent conductivity after modification. In terms of mechanical properties, the tensile strength of the fibers is maximally increased by 20.6%, highlighting the significant advantages of the method in preserving fiber structure and enhancing fiber mechanical performance. It was verified by variability analysis and Weibull distribution modeling. The investigation provides a new opportunity for expanding the application of basalt fibers and achieving functionalized basalt fiber composite materials.
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Key words:
- Basalt fiber /
- polypyrrole /
- electrical conductivity /
- in-situ polymerization method /
- dopant /
- tensile strength
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图 1 导电玄武岩纤维制备流程图
Figure 1. Flow chart for the preparation of conductive basalt fiber fabric
图 2 四探针法测电阻实验
Figure 2. Schematic diagram of four-probe method for resistance measurement experiment
图 3 纤维单丝拉伸实验：(a) 纤维单丝样品；(b) XQ-2纤维强伸度仪进行拉伸试验
Figure 3. Schematic diagram of single fiber tensile experiment: (a) single fiber sample; (b) tensile test with XQ-2 fiber strength instrumentation
图 4 聚吡咯/玄武岩纤维(PPy/BF)宏观形貌及形成过程示意图
Figure 4. Schematic diagram of polypyrrole/basalt fibers (PPy/BF) macroscopic morphology and formation process
图 5 FESEM图：(a) 未处理的玄武岩纤维；(b) 和 (c) 分别为PPy/BF-0.5和PPy/BF(1)；(d) PPy/BF-0.5上聚合生长的PPy颗粒；(e) 和 (f) PPy/BF(1)上聚合生长的PPy颗粒
Figure 5. FESEM image: (a) untreated basalt fibers; (b) and (c) PPy/BF-0.5 and PPy/BF(1), respectively; (d) PPy particles polymerized on PPy/BF-0.5; (e) and (f) PPy particles polymerized on PPy/BF(1)
图 6 (a)和(b)分别为PPy/BF(0)和PPy/BF(1)的N1 s分峰拟合图；(c) BF、PPy/BF(0)和PPy/BF(1)的XPS全谱图；(d) PPy/BF(0) 和PPy/BF(1)的Raman光谱图
Figure 6. N1 s region spectra of (a) PPy/BF(0) and (b) PPy/BF(1); (c) XPS full spectra of BF, PPy/BF(0), and PPy/BF(1); (d) Raman spectra of PPy/BF(0) and PPy/BF(1)
图 7 不同制备参数下PPy/BF的电阻率：(a) Py与FeCl3不同摩尔比的影响；(b) NaSSA与Py不同摩尔比的影响
Figure 7. Resistivity of PPy/BF under different preparation parameters: (a) effect of different molar ratios of Py to FeCl3; (b) effect of different molar ratios of NaSSA to Py
图 8 NaSSA与Fe3+反应生成紫色络合物方程式示意图
Figure 8. Schematic diagram of the equation for the reaction of NaSSA with Fe3+ to form a purple complex
图 9 BF和PPy/BF(1) 纤维单丝拉伸应力-应变曲线
Figure 9. Single Fiber Tensile Stress-Strain Curves of BF and PPy/BF(1)
图 10 BF和PPy/BF(1)纤维单丝拉伸强度Weibull双对数图
Figure 10. Weibull double logarithmic plot of monofilament fiber tensile strength of BF and PPy/BF(1)
表 1 XPS全谱图中BF、PPy/BF(0)和PPy/BF(1)表面元素及百分含量(at%)
Table 1. Surface elements and compositions (at%) of BF, PPy/BF(0) and PPy/BF(1) in the XPS spectra
Sample C O N Cl S Si (Cl+S)/N BF 48.81 39.61 \ \ \ 11.58 \ PPy/BF(0) 71.16 11.76 12.72 2.89 \ 1.47 0.23 PPy/BF(1) 63.51 20.36 9.5 3.09 2.34 1.21 0.57 
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表 2 Raman光谱中不同特征峰强度比
Table 2. Intensity ratios of different characteristic peaks in Raman spectra
Sample R1 R2 R3 L PPy/BF(0) 0.93 1.07 1.02 1.39 PPy/BF(1) 1.17 1.23 1.21 1.64 Note: R1 =$\frac{{I(938 \,\,{\rm{cm})^{ - 1}})}}{{I(980 \,\,{\rm{cm})^{ - 1}})}}$, R2 =$\frac{{I(1\,089 \,\,{\rm{cm})^{ - 1}})}}{{I(1\,055 \,\,{\rm{cm})^{ - 1}})}}$, R3 = $\frac{{I(938 \,\,{\rm{cm})^{ - 1}}) + I(1\,089 \,\,{\rm{cm})^{ - 1}})}}{{I(980 \,\,{\rm{cm})^{ - 1}}) + I(1\,055 \,\,{\rm{cm})^{ - 1}})}}$, L = $\frac{{I(1\,568 \,\,{\rm{cm})^{ - 1}})}}{{I(1\,500 \,\,{\rm{cm})^{ - 1}})}}$.
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表 3 PPy改性前后玄武岩纤维单丝拉伸强度
Table 3. Monofilament tensile strength of basalt fiber before and after PPy modification
Sample Monofilament Tensile Strength
/MPaDispersion Coefficient
/%Elastic Modulus
/GPaDispersion Coefficient
/%BF 2203 6.5 72.91 4.9 PPy/BF(1) 2657 7.1 74.85 5.2
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表 4 BF和PPy/BF单丝拉伸强度S-W检验
Table 4. The S-W test of BF and PPy/BF monofilament tensile strength
Sample w statistical indicator P value BF 0.943 0.213 PPy/BF(1) 0.969 0.672
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表 5 BF和PPy/BF单丝拉伸强度方差齐次性检验
Table 5. The F-test of BF and PPy/BF monofilament tensile strength
Sample F statistical indicator P value BF and PPy/BF(1) 2.63 0.112
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表 6 BF和PPy/BF单丝拉伸强度独立样本T检验
Table 6. The independent samples T-test of BF and PPy/BF monofilament tensile strength
Sample T statistical indicator P value Cohen's d value BF and PPy/BF(1) −3.571 0.001 1.053
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表 7 Weibull分布线性拟合结果
Table 7. Linear fitting results for the Weibull distribution
Sample Correlation coefficient (R) Shape parameter (β) Position parameter (η) BF 0.967 7.06 2359.70 PPy/BF 0.965 5.95 2872.20
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