Polyacrylonitrile precursor

Two different polyacrylonitrile precursor carbon fibers, an A fiber of low tensile modulus and an HM fiber of intermediate tensile modulus were characterized both as to their surface chemical and morphological composition as well as to their behavior in an epoxy matrix under interfacial shear loading conditions. The fiber surfaces were in two conditions. Untreated fibers were used as they were obtained from the reactors and surface treated fibers had a surface oxidative treatment applied to them. Quantitative differences in surface chemistry as well as interfacial shear strength were measur-ed. 

A substance (fibre) prepared from either pitch or polyacrylonitrile, precursors by oxidation-carbonisation and graphitisation processes. 

Moreton R, The removal of sodium from polyacrylonitrile precursor fibre and its effect on the mechanical properties of RAE carbon fibre, RAE Tech Memo MAT 78, Feb 1970. 

Moreton R, Spinning of polyacrylonitrile precursor fibres with reference to the properties of carbon fibres, 3" Conference, Industrial Carbons and Graphite, SCI, London, 1970. 

Tsai JS, Lin CH, The effect of molecular-weight on the cross-section and properties of polyacrylonitrile precursor and resulting carbon-fiber. Journal of Applied Polymer Science, 42, No.ll, 3045-3050, 1991. 

Rajalingham P, Radhakrishnan G, Polyacrylonitrile precursor for carbon-fibers, J Macromol Sci Rev Macromol Chem Phys, C31, No.2-3, 301-310, 1991. 

Tsai JS, Wu CJ, Effect of cross-section evenness for polyacrylonitrile precursor on properties of carbon-fiber, J Mater Sci Let, 12, No.6, 411 13, 1993. 

Tsai JS, Effect of drawing ratio during spinning and oxidation on the properties of polyacrylonitrile precursor and resulting carbon-fiber, J Mater Sci Lett, 11(3), 140-142, 1992. 

Liu J, Zhou P, Zhang L, Ma Z, Liang J, Fong H (2009) Thermo-chemical reactions occurring during the oxidative stabilization of electrospun polyacrylonitrile precursor nanofibers and the resulting structural conversions, Carbon 47 1087-1095. 

Jie, L. Wangxi, Z. Structural Changes during the Thermal Stabilization ofModified and Original Polyacrylonitrile Precursors. JApplPolym Sci 2005, 97,2047-2053. 

The various routes to ceramic fibres from organometallic preceramic polymers have a number of features in common, and bear similarities to industrial routes to high performance carbon fibres starting from polyacrylonitrile precursor fibres. 

For nosetip materials 3-directional-reinforced (3D) carbon preforms are formed using small cell sizes for uniform ablation and small pore size. Figure 5 shows typical unit cell dimensions for two of the most common 3D nosetip materials. Carbon-carbon woven preforms have been made with a variety of cell dimensions for different appHcations (27—33). Fibers common to these composites include rayon, polyacrylonitrile, and pitch precursor carbon fibers. Strength of these fibers ranges from 1 to 5 GPa (145,000—725,000 psi) and modulus ranges from 300 to 800 GPa. 

Process. Any standard precursor material can be used, but the preferred material is wet spun Courtaulds special acrylic fiber (SAF), oxidized by RK Carbon Fibers Co. to form 6K Panox B oxidized polyacrylonitrile (PAN) fiber (OPF). This OPF is treated ia a nitrogen atmosphere at 450—750°C, preferably 525—595°C, to give fibers having between 69—70% C, 19% N density less than 2.5 g/mL and a specific resistivity under 10 ° ohm-cm. If crimp is desired, the fibers are first knit iato a sock before heat treating and then de-knit. Controlled carbonization of precursor filaments results ia a linear Dow fiber (LDF), whereas controlled carbonization of knit precursor fibers results ia a curly carbonaceous fiber (EDF). At higher carbonizing temperatures of 1000—1400°C the fibers become electrically conductive (22). 

More than 95% of current carbon fiber production for advanced composite appHcations is based on the thermal conversion of polyacrylonitrile (PAN) or pitch precursors to carbon or graphite fibers. Generally, the conversion of PAN or pitch precursor to carbon fiber involves similar process steps fiber formation, ie, spinning, stabilization to thermoset the fiber, carbonization—graphitization, surface treatment, and sizing. Schematic process flow diagrams are shown in Eigure 4. However, specific process details differ. 

M. G. Dunham, Stabilisation of Polyacrylonitrile Carbon Fiber Precursors, Ph.D. dissertation, Clemson Urdversity, Clemson, S.C., May 1990. 

Because of their unique blend of properties, composites reinforced with high performance carbon fibers find use in many structural applications. However, it is possible to produce carbon fibers with very different properties, depending on the precursor used and processing conditions employed. Commercially, continuous high performance carbon fibers currently are formed from two precursor fibers, polyacrylonitrile (PAN) and mesophase pitch. The PAN-based carbon fiber dominates the ultra-high strength, high temperature fiber market (and represents about 90% of the total carbon fiber production), while the mesophase pitch fibers can achieve stiffnesses and thermal conductivities unsurpassed by any other continuous fiber. This chapter compares the processes, structures, and properties of these two classes of fibers. 

Because the polymer degrades before melting, polyacrylonitrile is commonly formed into fibers via a wet spinning process. The precursor is actually a copolymer of acrylonitrile and other monomer(s) which are added to control the oxidation rate and lower the glass transition temperature of the material. Common copolymers include vinyl acetate, methyl acrylate, methyl methacrylate, acrylic acid, itaconic acid, and methacrylic acid [1,2]. 

Dunham, M. G., Stabilization of polyacrylonitrile carbon fiber precursors. Ph.D. dissertation, Clemson University, Clemson, SC, 1990. 

On the other hand, organic materials of relatively low molecular weight such as acetylene, benzene, ethylene and methane, can produce vapour-grown carbon materials by imperfect combustion or by exposing their vapour to a heated substrate in an electric furnace in the presence of a metal catalyst. The latter process generates VGCFs. Other precursors to VGCF include polyacrylonitrile (PAN), isotropic or mesophase pitch, rayon or nylon [8]. 

The high purity carbon nanotubes (CNTs) used in this study were obtained by decomposition of acetylene over a powdered CoxMgi xO solid solution catalyst [19]. Different proportions of CNTs from 15 to 70% and polyacrylonitrile (PAN, Aldrich) have been mixed in an excess of acetone to obtain a slurry. After evaporation of acetone, precursor electrodes were formed by pressing the CNTs/PAN mixture at 1-2 tons/cm2. The C/C composites were formed by carbonisation of the pellets at 700-900°C for 30-420 min under nitrogen flow [20], The optimal capacitance properties of the composite were obtained for a mixture CNTs/PAN (30/70 wt%) treated at 700°C. Such C/C composite remains still quite rich in nitrogen (9 at% of N) demonstrating that PAN is an efficient nitrogen carrier. On the other hand,... 

CNF is an industrially produced derivative of carbon formed by the decomposition and graphitization of rich organic carbon polymers (Fig. 14.3). The most common precursor is polyacrylonitrile (PAN), as it yields high tensile and compressive strength fibers that have high resistance to corrosion, creep and fatigue. For these reasons, the fibers are widely used in the automotive and aerospace industries [1], Carbon fiber is an important ingredient of carbon composite materials, which are used in fuel cell construction, particularly in gas-diffusion layers where the fibers are woven to form a type of carbon cloth. 

The production of carbon fibres is based on the pyrolysis of organic fibres or precursors. The main starting materials are polyacrylonitrile (PAN) and pitch (coal tar or petroleum asphalt). They can be classified according to their mechanical performances ... 

The surface properties of carbon fibers are intimately related to the internal structure of the fiber itself, which needs to be understood if the surface properties are to be modified for specific end applications. Carbon fibers have been made from a number of different precursors, including polyacrylonitrile (PAN), rayon (cellulose) and mesophase pitch. The majority of commercial carbon fibers currently produced are based on PAN, while those based on rayon and pitch are produced in very limited quantities for special applications. Therefore, the discussion of fiber surface treatments in this section is mostly related to PAN-based carbon fibers, unless otherwise specified. 

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