열수 연신시 흑연화 촉매 도입에 따른 탄소섬유의 흑연화 촉진효과
Catalytic Effects on Graphitized Carbon Fibers of Graphitization Catalysts Introduced during Hot-Water Stretching
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초록
본 논문에서는 습식 방사 공정을 통한 PAN(polyacrylonitrile)계 전구체 섬유의 형태학적 제어 및 2종의 흑연화 촉진제(Ca, Ni)가 도입된 PAN계 탄소섬유의 흑연화 거동을 조사하였다. 흑연화 촉진제는 습식방사된 PAN계 전구체 섬유의 열수 연신시 형성된 기공으로 도입되었으며, 결정구조 및 라만 분석을 통해 흑연화 촉진효과를 검토하였다. 1500℃의 상대적으로 낮은 온도에서는 흑연화에 큰 영향을 주지 않은 반면에, 2400℃의 고온에서는 흑연화 촉진제 미처리 섬유와 비교하여 ID/IG 비율이 최대 2배까지 감소하는(GF-AS 0.54: GF-Ni100 0.28) 경향을 나타냈다. 흑연화도(degree of graphitization)는 Ca 흑연화 촉진제와 비교하여 Ni 흑연화 촉진제가 더 큰 영향을 끼침을 ID/IG 비율을 비교하여(GF-Ca100 0.42: GF-Ni100 0.28) 확인할 수 있었다. 또한, 2D band의 존재로부터 흑연평면구조가 다층으로 구성되어져 있음을 알 수 있었다. 흑연결정의 결정면간거리(d002)에 대한 흑연화 촉진제 효과는 미비하였으나, 특히 Ca 흑연화 촉진제 처리된 흑연섬유(GF-Ca100)의 경우 최대 ~ 5 nm 결정 크기가 증가함이 확인되었다.
Abstract
In this study, PAN(polyacrylonitrile)-based precursor fibers were produced through a wet-spinning process, and their morphologies and graphitization behavior were investigated in the presence of two graphitization catalysts (Ca, Ni). The graphitization catalysts were introduced into the formed pores during hot-water stretching of wet-spun PAN-based precursor fibers. The catalytic effects of graphitization catalysts were examined through crystal structure and Raman analysis. At a relatively low temperature of 1500°C, the graphitization was not significantly affected, whereas at a high temperature of 2400°C, the obtained ID/IG value of graphite fiber (GF-Ni100) was decreased by about twice (~ 0.28) compared to the untreated fibers (GF-AS ~ 0.54). By comparing the ID/IG values (GF-Ca100 ~ 0.42: GF-Ni100 ~ 0.28) of Ca and Ni graphitization catalyst, it was found that the degree of graphitization of Ni graphitization catalyst showed higher influence than that of Ca graphitization catalyst. Moreover, 2D band was also observed, indicating that the graphite plane structures composed of multiple layers were developed. XRD results confirmed that the crystal inter-planar distance (d002) of the graphite crystal was slightly decreased after the treatment with the graphitization catalyst, But, the crystal size of Ca-treated graphite fiber (GF-Ca100) was increased by up to ~ 5 nm.
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