NEW CARBON MATERIALS

Volume 24, Issue 1, March 2009 Online English edition of the Chinese language journal Cite this article as: New Carbon Materials, 2009, 24(1):8388. RESEARCH PAPER

Preparation and characterization of pitch-based carbon fibers

Abstract: A petroleum pitch was heated at 420 oC for 7 h in nitrogen to prepare a carbon fiber precursor with a softening point of 295
o

C. The precursor was successfully melt-spun into fibers through a circular nozzle of a monofilament spinning apparatus, and these were

then stabilized at 320 oC in air and finally carbonized at 1000 oC in nitrogen to produce carbon fibers. SEM, TGA, FT-IR, and XRD were performed to characterize the petroleum pitch, the precursor, the as-spun fibers, the stabilized fibers, and the carbon fibers. It is found that the precursor contains 70.5% mass fraction of mesophase that is aligned upon spinning, and aliphatic side chains that are beneficial to spinning. The carbon fibers have a radial core structure with a linear and bent type anisotropic texture. The maximum tensile strength of the carbon fiber is 650 MPa. Key Words: Precursor pitch, Carbon fiber, Photomicroscopy, X-ray diffractometry

Introduction

Carbon fibers are considered to be high strength materials having great importance in a variety of specialized applications, such as aerospace, automobile, chemical industry, general engineering, missile, nuclear field, reinforcement in composite materials, and textile. The importance of these materials in the above mentioned applications is based on their properties, such as high strength, high stiffness, dimensional stability, low coefficient of thermal expansion, biological compatibility, and fatigue resistance[1-2]. They can be classified according to their precursors[3-5] into polyacrylonitrile (PAN)-based carbon fibers, rayon-based carbon fibers, and pitch-based carbon fibers. Pitch-based carbon fibers can be further classified into high performance carbon fibers (HPCFs) and general purpose carbon fibers (GPCFs) according to their mechanical properties, which are prepared, respectively, from optically anisotropic pitch and isotropic pitch[6-9]. Wang et al.[10] reported the preparation of pitch fibers from petroleum pitch. They carried out an extensive optimization of the experimental conditions to obtain hollow fibers from mesophase pitch and found that die-swell was the major factor affecting the properties of the final product. Similarly, Park et al.[11] used an improved method for the production of carbon fibers. In this case, the precursor pitch was melt-spun by means of pressurized nitrogen through specialized gadgets, which was ultimately carbonized into the desired carbon fibers at the elevated temperatures. The same methodology for mak-

ing carbon fibers was also used by Fumitaka et al.[12]. However, the latter investigations also focused on studying the melt spinning of a synthetic isotropic pitch containing mesophase spheres to produce carbon fibers with high compressive strength. The present work deals with the conversion of Pakistani petroleum pitch obtained from Attock Refinery Limited (ARL), Rawalpindi, Pakistan, into a spinnable pitch by thermal condensation, which is melt-spun to produce carbon fibers. The aim of this study is focused on optimizing the operating conditions for melt-spinning of the precursor pitch. The detailed analysis of the precursor pitch and melt-spun carbon fibers using FTIR, XRD, and optical microscopy is also performed.

2
2.1

Experimental
Materials

Petroleum pitch was indigenously provided by Attock Refinery Limited (ARL), Morgah, Rawalpindi, Pakistan. Organic solvents, such as benzene and quinoline, used were all of analytical grade reagents (Merck Company). 2.2 Preparation of precursor pitch A precursor pitch was prepared by thermal condensation of 100 g petroleum pitch at 420 oC for 7 h in a stirring reactor under nitrogen flow. The soluble and insoluble fractions of the precursor pitch were separated by soxlet extraction using benzene and quinoline as solvents. The product yield was

Received date: 17 December 2008; Revised date: 3 March 2009 *Corresponding author. E-mail: arshkhpk@[Link]/arshadwaziri@[Link] Copyright2009, Institute of Coal Chemistry, Chinese Academy of Sciences. Published by Elsevier Limited. All rights reserved. DOI: 10.1016/S1872-5805(08)60039-6

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and the O content was calculated by subtracting the sum of C, H, and N (%) from 100. Thermogravimetric analysis (TGA 1640, Stanton Redcroft, Canada) of samples was performed under air and nitrogen atmosphere to find an optimum stabilization temperature or to measure the thermal stability of the samples. The polished section on glass slide of the precursor pitch and the longitudinal sections of the melt-spun fibers were observed under a polarized-light microscope (Olympus Model-CX21FS1 Philippine, Japan). The melt-spun fibers were also examined by Scanning Electron Microscope (FE-SEM S-4700, Hitachi, Japan). Infra Red Spectroscopy (FT-IR Spectrometer, model Perkin Elmer 16pc) was used to characterize the functional groups of both the petroleum pitch and the precursor pitch and extracted mesophase pitch. The precursor pitch and melt spun fiber samples in powder form were used in the X-ray diffraction (XRD) analysis. The XRD patterns of the samples were obtained by a diffractometer (JEOL X-ray diffractometer, model JDX-73) using Mn-filtered Cu-K as radiation. For tensile strength measurements, 2.5 cm sample was loaded and measured by a tensile tester with a 150 g load and at a cross head speed of 2.5 mm/min. An average was taken from the five tests on the bases of JIS R 7601 method.

Fig.1 Schematic diagrams of the reactor and the melt-spinning apparatus

calculated by applying the equation (1). Yield (%) = Mass of the precursor/ Mass of the petroleum pitch 100 . (1) The schematic diagrams of the reactor and the melt-spinning apparatus are shown in Fig.1. 2.3 Preparation of carbon fibers A laboratory scale apparatus was used to melt-spin the precursor pitch into carbon fibers under pressurized nitrogen of 2 kg/cm2 through a mono-hole spinneret (D = 0.4 mm) at a spinning temperature of 335 oC. The as-spun fibers were stabilized at 320 oC for 2 h in air with a heating rate of 2 oC /min. The stabilized fibers were further carbonized at 1000 oC for 1 h under nitrogen flow in a tube furnace at a heating rate of 5 o C /min. The carbon yield was calculated by applying the equation (2).

Results and discussion

3.1 Preparation of carbon fibers 3.1.1 Preparation of precursor pitch

Carbon yield (%)=Mass of the carbonized fibers/ Mass of the stabilized fibers100.
2.4 Characterization

(2)

Metler FP 90 apparatus (Metler Toledo AG, Switzerland, ASTMD3140) was used to determine softening point of samples. Benzene soluble (BS), benzene insoluble (BI), benzene insoluble-quinoline soluble (BI-QS), and quinoline insoluble (QI) fractions of the pitches were measured by the soxlet extraction. The contents of C, H, and N in samples were determined by an elemental analyzer (EA 1110, CE Instruments, Italia),

Properties of the precursor pitch are summarized in Table 1. The soluble parts are considered to be isotropic in nature, whereas the insoluble parts are anisotropic. During heat treatment of pitch at 400-450 oC, anisotropic spheres called mesophase are developed in the isotropic pitch matrix like a liquid droplet inside a liquid, as described by Brooks and Taylor[13]. Their optical anisotropy and micrometer scale structure can be well observed under a polarized light microscope on the polished sections. These spheres coalesce and form a mosaic-like nematic liquid-crystal structure, which is still plastic and called bulk mesophase[14] with a prolonged heat treatment time. With furthermore heat treatment, the mesophase develops into highly graphitizable carbon, and the mobility of the individual molecule is confined because of the rigidity of the highly ordered solid phase[15].
Table 1 Properties of precursor pitch Softeningpoint 295 quinoline insoluble. t/ oC Solubility w/% BS 5.4 BI-QS 20.3 QI 75.2

*BS: benzene soluble, BI-QS: benzene insoluble-quinoline soluble,QI:

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Fig.2

Polarized light microphotographs of (a) precursor pitch showing the mesophase sphere formation, (b) the longitudinal surface of spun fiber, and (c) the cross section of spun fiber

Fig.3 SEM microphotographs of (a) stabilized fiber, (b) carbonized fiber at 1000 oC and (c) cross sectional area of carbonized fiber with high magnification

The isotropic pitch is composed mainly of polyaromatic hydrocarbons along with many aliphatic side-chains. The disordered phase of the isotropic pitch become more and more ordered because of the removal of low weight volatile components during heat treatment. The texture of the graphitizable carbon depends upon the material structure during transformation into liquid crystalline state. The nucleation, growth, and texturing of the mesophase pitch are strongly dependent upon preparation method, rheological properties of the precursors, and heat treatment temperature[16]. It is considered that mesophase pitch having high molecular weight components without any side groups or small molecular components is difficult to be melt-spun. Therefore, a mesophase pitch containing a small amount of low molecular weight side groups that cause disordering texture is easier to be melt-spun to form fibers[17]. The polished section on glass slide of precursor pitch shows the mesophase sphere formation as shown by the polarized light microscope in the Fig.2(a). The precursor pitch was found to be composed of 75% mass fraction mesophase, which was successfully melt-spun into fibers. The elemental analysis results of samples in the process of carbon fiber formation are listed in Table 2. It can be found that C, H, and the H/C ratio decreases, whereas N and O increase gradually with processing before carbonization. The contents of H, N, and O,

and the H/C ratio decrease abruptly and C content increase by carbonization. The existence of relatively high concentration of low molecular weight components of alkyl groups can be derived from the fact that a high uptake of oxygen (16.5 %) was found during stabilization. 3.1.2 Melt spinning

High performance pitch fibers are prepared from mesophase pitch having liquid-crystal characteristics. The liquid crystalline in the pitch can be readily oriented to produce highly oriented texture of fibers during melt spinning. The resulting fibers in their as-spun and stabilized state show highly oriented X-ray reflections, which are similar to the (002) reflection of graphite crystal[18]. Fig.2(b) and (c) shows, respectively, the as-spun fiber and its cross section under the polarized light microscope. Fig.3(a) and (b) show, respectively, the cross sections of the stabilized fiber and carbon fiber. The carbon fiber showed a typical radial core structure[11-12, 19]. The transverse texture of the cross-sectional area of the carbon fiber under a high magnification is also shown in Fig.3(c), indicating a typical radial core structure with linear and bent type anisotropic texture. This structure is also considered to be dependent upon the spinning conditions and the properties of the precursor pitch[20].

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and 1370 cm-1[21-23]. The numerous bands in the wave numbers regions 3031 and 1680-1462 cm-1 can be assigned to stretching of aromatic C=C bonds. The bands that can be seen at wave numbers 2900-2700 cm-1 and 1370 cm-1 are assigned to the stretching and bending modes of saturated aliphatic hydrocarbons. The band can be seen at wave number 2348 cm-1, which corresponds to CO2. The bands at wave numbers 930, 855, 810, and 730 cm-1, can be ascribed to the out-of-plane bending of aromatic CH groups[24-25]. A weak band at wave numbers 1088 and 1012 cm-1 can be observed, which can be attributable to the aryl group.
Fig.4 TGA curve of pitch fibers Table 2 Elemental analyses of the precursor pitch and pitch fibers at various conditions Sample Precursor Pitch As-spun fiber Stabilized fiber Carbonized fiber H/C (Atom ratio ) 0.54 0.53 0.41 0.02 Elemental C 92.03 90.40 80.13 95.90 H 4.36 4.25 2.91 0.16 N 0.35 0.40 0.45 00 w/% O 3.26 4.95 16.51 3.92

The FT-IR spectrum of the extracted mesophase pitch is given in the Fig.5(b). The spectrum contains similar peaks relative to the precursor pitch. Numerous bands that can be seen at wave numbers 3042, 1600, 930, 875, 815, and 750 cm-1 are assigned to the presence of aromatic CH stretching and out of plane deformation of aromatic ring. Bands can be seen in wave numbers 2921, 2832, 2720, 1445, and 1370 cm-1, which can be ascribed to the presence of aliphatic CH stretching and methylene CH (probably naphthenic) bending modes[21-25]. The more intense band at wave number 1445 cm-1 indicates that the material has methylene or naphthene rich structure. Comparatively, on the basis of separating soluble contents from the precursor pitch, the intensity of the bands at wave numbers 750-875 cm-1 are slightly increased compared with the precursor pitch, owing to a significant increase in aromatic contents. This qualitative evidence of the low molecular weight aliphatics with high contents of aromatics is in accordance with the good spinnablity of the mesophase pitch. 3.4 X-ray diffractometry The XRD patterns of precursor pitch, the as-spun fiber, the stabilized fiber, and carbon fiber are shown in Fig.6, which show a distinct reflection band at 2 of 25.65o, 25.75o, 25.55o, and 24.6o, respectively. This can be accounted for by the presence of graphitic structure in these samples. The interlayer spacings (d002) of precursor pitch, the as-spun fiber, the stabilized fiber and carbon fiber are shown in the Fig.7. It can be found that the d 002 -spacings is decreased by orienting the

3.2

Thermogravimetric analysis

As it is well known that during the oxidation process, oxygen tends to react first with aliphatic side groups. Therefore, the stabilization behaviors are dependent on the pitch reactivity, and the higher the oxygen uptake, the more the aliphatic side-groups and the lower the aromaticity of pitch. As shown in Fig.4, the oxygen uptake started at 200 oC until 450 oC, at which evident combustion occurs. The carbon yield of 70.5% can be obtained by residue mass above 600 oC under nitrogen. 3.3 FT-IR analysis

The profile of the FT-IR spectrum of unextracted precursor pitch is provided in Fig. 5(a). The characteristic bands can be seen in the wave number region corresponding to the aromatic structures at 3031, 1680, 1600, 838, 855, 810, and 730 cm-1 and aliphatic structures at 2915, 2840, 2718, 1595, 1462,

Fig.5 FT-IR profiles of (a) precursor pitch and (b) extracted mesophase pitch

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fibers shows the highest tensile strength of approximately 650 MPa among all kinds of fibers tested.

Conclusions

Fig.6 XRD profiles of precursor pitch containing mesophase pitch, as-spun carbon fiber, stabilized carbon fiber and carbonized carbon fiber at 1000 oC

The precursor pitch was prepared from petroleum pitch by condensation at 420 oC for 7 h, which was composed of 75% mass fraction mesophase and had a carbon yield of approximately 70.5% with a softening point of 295 oC. The precursor pitch showed good spinnability with a wind up speed of 250 m/min. The precursor pitch contains mesophase spheres. A typical radial core structure was formed in carbon fibers by carbonization at 1000 oC, which had a tensile strength of 650 MPa. The petroleum-based precursor pitch is suitable for the preparation of carbon fibers. Acknowledgment The present work is supported by Higher Education Commission of Pakistan for the promotion of Science [The Grant-in-Aid for Scientific Research Project No. 20-377/R & D/05/1057].

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