Manufacturing of Carbon Fibers

By- Viplav Singh 2010TT10974 Group-2

Introduction: Carbon fibers can be prepared from polymeric precursor materials such as polyacrylonitrile (PAN), cellulose, pitch and polyvinylchloride, which are discussed in detail later. PAN based carbon fibers predominate and have good strength and modulus properties, whereas carbon fiber can be made with a higher modulus, albeit a lower strength, using a pitch-based precursor. Carbon Fibers: These are fibers(filaments, tows, yarns, rovings) consisting of at least 92% (mass fraction) carbon, usually in the non-graphitic state. Carbon fiber HT are carbon fiber with values of Youngs Modulus in the range 150275 or 300 GPa. The term HT, referring to high tensile strength, was previously applied because fibers of this type display the highest tensile strengths.

There have been various types of carbon fibers, some of wich were discovered quit early. Nowdays this field has become very advance and atteractive. Some of these fiberous forms of carbon are :1. GRAPHITE WHISKERS :- While handling hydrocarbon gases in equipments at temperature of 350o 2500oC, graphite filaments forming upto 200 mm in diameter and about 50 mm long have been observed, ranging from solid filaments to helices and hollow tubes.

2. VAPOR-GROWN CARBON FIBERS (VGCF) & CATALYTIC CHEMICAL VAPOR-DEPOSITED (CCVD) FILAMENTS :- (Discussed latter) 3. CARBON NANOTUBES :- Carbon nano tubes are allotropes of carbon with a cylindrical nano structure. Nano tubes have been constructed with lenght to diameter ratio upto 132,000,000:1 significantly. The have extraordanery thermal conductivity and electrical properties. These nano tubes are made by arc discharge, laser ablation, chemical vapor deposetion(CVD) etc.

Precursors for Carbon Fiber Manufacture

Carbon Fiber Production using a PAN Precursor :
A PAN based carbon fiber is produced by the oxidative stabilization of a PAN precursor, normally followed by a two-stage carbonization process, with an added heat treatment stage to manufacture a high modulus fiber. The aim is to remove, in gaseous form, all elements other than carbon, although high strength fibers do contain up to about 5% nitrogen, depending on the manufacturer. Desirable Attributes of a PAN Based Precusor Polymer : A copolymer must have acrylonitrile content greater than 85%, preferably 9095%. The number average molecular weight should be 40,00070,000 g mole1 preferably, which is about 1000 repeat units. The weight average molecular weight is preferably about 90,000140,000 and a value of 100,000, with an even distribution, would give a precursor fiber with good mechanical properties. A polydispersity index (Mw/Mn) of 1.53.0 is preferred. The polymer dope concentration in the spinning solvent is normally about 15% w/w .

Carbon Fiber Production Line:

Oxidation:- The acrylic precursor is stabilized by controlled low temperature heating

(200o300o C) in air to convert the precursor to a form that can be further heat treated without the occurrence of melting or fusion of the fibers. Oxidized PAN fiber of density 1.371.40 g cm3 is treated with a water based proprietary antistat finish, dried and collected after plaiting, into boxes positioned on a plaiter table with longitudinal and transverse movements to plait the opf neatly into the boxes without entanglement.

Low Temperature Carbonization :- The LT furnace can best be described as a tar

removal furnace and normally comprises a multizone electrically heated slot furnace (Figure 10.9), purged with N2 to prevent ingress of air and providing sufficient N2 flow to remove evolved tars and gases. The temperature in the furnace is gradually increased in the zones to a final temperature of about 950o C, a temperature above which the tars are decomposed leading to the deposition of a sooty product on the fiber, which causes the filaments to stick together and the carbon fiber properties to plummet.

High Temperature Carbonization :- Basically, the high temperature furnace

elevates the temperature in a uniform manner to increase the fiber modulus and a smaller dtex fiber will give a higher modulus for a given residence time, but lesser yield. The product formed during carbonization is a good conductor and imposes no limitation on the heating rate by heat transfer . Heating rates above 20 oC per minute and temperatures above 1500o C will impair the strength of the resulting carbon fibers.

Surface Treatment :- It is convenient to use an electrolytic surface treatment

process, which permits a good measure of control to be exercised. A suitable water soluble electrolyte is chosen, giving a solution that is readily conductive. The carbon fiber is made the anode and passed close and parallel to graphite cathodes without touching.

Sizing :- Initially solvent based sizes were used which gave excellent inter-filament
penetration, but were discontinued on health and cost grounds. Invariably, the present sizes are water based emulsions, preferably using the same chemical class as the ultimate polymer matrix.

Brief Machenism

From the IR spectrum of a PAN powder it was found at that 200 and 260 oC, the band in the spectrum assigned to the nitrile group gradually disappeared, coinciding with the appearance of a band attributed to a conjugated C=N grouping.

Carbon Fiber Production using a Cellulosic based Precursor :

Simplified stages for the conversion of cellulose to carbon: Physical desorption of about 12% absorbed water (25150 oC) with a small degree of change in lateral order. Dehydration from the H and OH fragments present in the cellulose unit (150240 oC). Thermal cleavage of the glycosidic linkage and scission of other C=O and some CC bonds via a free radical reaction (240400 oC) which leads to the formation of large amounts of tar, H2O, CO and CO2. Aromatization (400 oC and above) where each cellulose unit breaks down into a residue containing four C atoms which then polymerize through condensation reactions involving the removal of H above 400 oC into a C-polymer with an ultimate graphite-like structure. Choice of a suitable precursor : The basic composition of a rayon precursor, is the same as the original cellulose starting material (Cellulose I) . To make a continuous carbon fiber, a continuous viscose rayon fiber is required, which immediately imposes a limitation, since the majority of current viscose production is chopped to form a staple product.

Current Production:

Pyrolysis :- At elevated temperatures, a cellulosic precursor will break down into

highly volatile gases, a tarry distillate and a carbon char. The two reactions below are competitive, but since the withdrawal of the CH2OH groups starts at 120 oC, the early removal of these groups will prevent their subsequent reaction to form the undesirable levoglucosan at 250 oC. Hence, holding the temperature in the initial stages below 250 oC is an effective way of improving the carbon yield .

Carbonization :- The pyrolyzed fiber is then subjected to carbonization(the

conversation of an organic substance into carbon or a carbon containing residue. It is not feasible to run a continuous process carbonization stage in tandem with a prolonged pyrolysis stage. Therefore, it is practical to run the pyrolysis stage as a batch process and the furnace stages continuously. There are good reasons for separating carbonization into low and high temperature stages,.

Hot stretching during processing of carbon fiber :- The early fiber made from a
cellulosic precursor had a low modulus and manufacturers had to resort to hot stretching to orient the fine structure of the fiber and obtain a significant improvement of modulus, albeit at a cost.

Sizing:- As in earlier case.

Carbon Fiber Production using a Pitch based Precursor :Pitch is a general name for the tarry substance, which is solid at room temperature and can be obtained from one of several sources: Petroleum refining, normally called bitumen, Destructive distillation of coal , Natural asphalt, Pyrolysis of PVC , Pyrolysis of ring compounds, such as naphthalene and anthracene .

Choice of Melt Spun Precusor: An isotropic pitch precursor is used to make a GP grade carbon fiber . A mesophase pitch will produce a HP carbon fiber that can, if necessary, also be made from the same grade of isotropic pitch feedstock.

Manufacturing Process:

Stabilization (thermosetting) of spun fiber :- The pitch precursor fibers, as spun,

are very weak and almost without exception, thermoplastic in nature, making it imperative that they are chemically treated to render them suitable for subsequent carbonization. This is best accomplished by some form of oxidation treatment .

Carbonization:- Initially low temperature carbonization is done to avoid disruption

of the fiber structure. Normally, about 30 s to 5 min is sufficient time, while suitable treatment would be about 0.5 min at 700 oC followed by 0.5 min at 900 oC in an inert N2 atmosphere. A typical carbonizing furnace using a graphite hairpin element and capable of achieving 2000 oC . Carbonization is required to remove hetero-

atoms like H, N, O and S in the form of H2O, CO2, CO, N2, SO2, CH4, H2

and tars.
Diagram of a hairpin element furnace used to carbonize mesophase pitch fibers.

Graphitization :- A mesophase pitch based fiber can be further heat treated in a

similar type of furnace, using highly controlled inert atmosphere, at temperatures in the range 25003300 C, preferably 28003000 C, producing fibers with a high degree of orientation, where the carbon crystallites are parallel to the fiber axis. These fibers are truly graphitic and have a structure characteristic of polycrystalline graphite with a three-dimensional order.

Production of Vapor Grown Carbon Fibers (VGCF)

Tthere are in general three classes of VGCF: 1. Conventional filaments0.01 mm in diameter and 1 mm in length . 2. Very long precursor filaments which are the precursors for VGCFabout 0.01 mm in diameter and !1 mm in length . 3. VGCF resulting from thickening of the precursor filaments!1 mm in diameter and ! 1 mm in length .

Preparation of VGCF:- A batch process for producing VGCF using the apparatus
depicted in figure depositing the filaments on a series of nested semi-cylindrical mullite tubes of analysis- Al2O3 58.6%, SiO2 36.8%, Fe2O3 0.9%, TiO2 0.9%, CaO/MgO 0.8%, Na2O/K2O 1.32%, Balance 0.68%.

An apparatus for growing VGCF at atmospheric pressure.

Groth Process:- Many versions of possible growth mechanisms have been proposed. The
fiber consists of basal planes nesting together as a series of concentric cylinders so that a transverse cross- section resembles the growth rings of a tree rather than a scroll type of formation as obtained with carbon whiskers.

Mechanism of fiber growth. (1) Solid catalyst particle. (2) Short filament having grown on a solid particle. (3) Short filament on the liquid particle. (4) Rapid lengthening. (5) Fiber.

The most common mechanism of carbon filament formation from the pyrolysis of acetylene (C2H2) on a metal particle (M) where (C) denotes carbon.

Mechanism of carbon filament formation in the Pt/Fe system by extruded filament growth.

Surface Treatment and Sizing of Carbon Fibers

Oxidative Process:- Surface treatment is done by oxidation, involves gas phase, liquid
phase and anodic oxidation.

Plasma:- Plasma 'a fourth state of mater' being highly energetic has its application in surface
treatment. Plasma surface treatment is a dry reaction process and depending on the process conditions, can have ,surface cleaning removal of surface layer, penetrates the top few molecular layers and modifies the surface.

Non-Oxidative Surface Treatment-Whiskerization:- Whiskerization involves the

growth of minute single crystals, such as SiC, Si3N4 and TiO2 at right angles to the fiber surface in order to promote bonding between the fiber and resin in a composite.

References:1. Morgan Peter, Carbon Fiber and their Composites. 2. Frushhour BG, Knorr RS, Acrylic fibers, Lewin M and Pearce EM eds., Handbook of Fiber Chemistry, Marcel Dekker, New York, 8691070, 1998. 3. Olive GH, Olive S, The chemistry of carbon fiber formation from polyacrylonitrile, Adv Polym Sci, 51, 160, 1983. 4. Tibbetts GG, Vapor-grown carbon fibers: status and prospects, Carbon, 1989.