Cwhon Vol. 29, No 2. pp 251~269, 1991 Prmtcd m Orcat l3ntsin.

Copyright

00084223:Y (_ 1991 Pqamon

(I:1 + 00 I $3
Prcs5 plc

INFLUENCE OF BORON ON CARBON FIBER MICROSTRUCTURE, PHYSICAL PROPERTIES, AND OXIDATION BEHAVIOR
Department

L. E. JONES and P. A. THROWER of Materials Science and Engineering. The Pennsylvania State University, University Park, PA 16802
(Received 13 Februar_y 1990: accepted 11 May lY30)

Abstract-An investigation was conducted to determine the influence of substitutional boron on carbon fiber microstructure, physical properties. and oxidation behavior in 0.1 MPa UHP Cl?. Mesophase pitch P5.5and PAN T-3OOcarbon fibers were substitutionally doped with boron at concentration levels between 4 x 10m5and 0.05 B/C atom ratio. Boron was found to enhance graphitization in these fibers at concentrations greater than 2 x 10Y B/C. Below this concentration level the fiber microstructure and strength were unaffected. The presence of boron at all concentration levels inhibited carbon fiber oxidation. Oxidation inhibition at high boron concentrations was attributed to changes in the fiber microstructure and specific site blockage by an oxide of boron which developed on the fiber surface during gasification. At relatively low boron concentrations, the decrease in the reactivity of the fiber was related to a change in the fibers electronic structure which, in turn, influenced the chemistry of the active sites. Boron was also found to significantly influence the fiber structure. Boron modulated the (002) reflection by enhancing the development of two separate microstructures in the same fiber. one more oxidation resistant than the other. The room temperature mechanical properties of these doped fibers were relatively unaffected up to 5 x 10 B/C. hut strength and modulus sharply decreased above this dopant level.

Key Words-Carbon

fibers. boron. oxidation. mechanical properties.

1. INTRODUCTION

Carbon-carbon (C-C) composites have found increasing applications in both the aerospace and the

utiftiy communities because of their light weight and high performance. They possess specific strengths and moduli which are greater than other materials at elevated temperatures (with the possible exception of beryllium composites). The demand for lightweight, high-performance materials has placed a premium on understanding the fundamental processes affecting their high-temperature heterogeneous reactions with the surrounding environment and developing a means of protecting them from oxidation. It is well established that although C-C composites possess uniquely superior mechanical properties, the high-temperature application of carbon fiber reinforced composites is limited by carbon oxidation. Under oxidizing conditions at temperatures of 770 K or higher, carbon readily chemisorbs oxygen and subsequently desorbs oxides of carbon. This oxidation process results in the erosion of the structure and eventually in the degradation of the properties which the material originally possessed. This problem is especially acute for those applications which require materials survivability at high temperatures and during repeated thermal cycling in environments containing steam, oxygen, CO?, or unburned hydrocarbons. Therefore, one of the critical issues in the application of structural carbon materials is the in251

hibition of carbon oxidation. The protection of citrbon-carbon composites from oxidation has been studied by many researchers. Much of this research is not available in the open literature; however, a few complete discussions have been published, most notably by McKee et al.[l.Z] and Strife and Sheehan[3]. Very few of these studies have attempted to address the kinetics of carbon-carbon oxidation and the mechanisms operative during oxidation inhibition. One such laboratory study on the reactivity of C-C in H10iH2 gas mixtures showed that this composites reactivity at 973 K was strongly in~uenced by the carbon fiber used in the fabrication. It was found that composites fabricated with PAN T-300 fibers were roughly three times more reactive than composites fabricated with pitch P55 fibers[4]. The significance of carbon fiber oxidation can also be seen on the surface of three-dimensional C-C composites used as nozzles for rockets[ilj. These materials, when exposed to the product of combustion from a solid propellant, may reach surface temperatures approaching 3,300 K and pressures as high as 5 MPa. The postfired composite samples exhibit preferential surface oxidation. Fiber ends exposed on the surface were attacked preferentially by the oxidizing environment resulting in a pockmarked surface topography. The cause of this preferential attack under conditions which were clearly transport limited were unclear. However, it is generally understood that the chemistry and structure of the carbon fiber ends is quite different than those of the sur-

252

L. E. JONES and P. A. THROWER been previously shown to be a strong inhibitor of bulk graphite oxidation[5], where it was clearly shown to inhibit the oxidation rate by decreasing the activation energy of the reaction. This paper describes the influence of substitutionally doped boron on the microstructure, physical properties, mechanical behavior, and reactivity of typical pitch and PAN carbon fibers.

rounding carbon matrix and the outer carbon fiber surfaces. This suggests that the surface chemistry of the C-C composite had an influence on oxidation even under the extreme conditions typical of a nozzle throat at the postfired end of a solid propellant rocket, and that the preferential oxidation of carbon fibers as dictated by their orientation in the composite is a significant consideration in the overall understanding of the carbon-carbon oxidation process. The impact of carbon fiber oxidation has become increasingly more important in the application of current advanced carbon-carbon composites in which the matrix is protected through the addition of glass forming inhibitors such as B,O, which melt at relatively low temperatures and flow to fill cracks in the matrix, providing a diffusion barrier in the composite. In these materials oxidation also occurs preferentially at the fiber ends and/or along the fiber length. The carbon matrix is protected because the diffusion of oxygen into and through the matrix is impeded by these in-situ glassy sealants which fill any porosity whether original or developed during oxidation. Currently, little is done to retard the oxidation of the fibers, and they tend to hollow out during hightemperature use, leaving behind a sheath of stabilized outer fiber skin and matrix material. From these results, it can be argued that fiber oxidation is critical in these structural composites and that achieving an understanding of fiber oxidation behavior is one key toward achieving enhanced overall C-C composite oxidation resistance. This study was conducted to address composite recession in terms of the relationship between oxidation behavior, microstructure, and physical properties of the carbon fibers typically used in the fabrication of carbon-carbon composites. The objective of this study was to establish that carbon fiber oxidation can be inhibited through the use of substitutional dopants and to evaluate the impact of the oxidation inhibitors on the fiber microstructure and the subsequent mechanical properties. Boron was the dopant of interest because it had

2.

EXPERIMENTAL

2.1 Materials Two carbon fibers were examined, a mesophase pitch (P55) fiber and a polyacrylonitrile (PAN T300) fiber, which were both manufactured by Amoco Performance Products. The research initially focused on fiber oxidation and on the inhibition of the oxidation by substitutionally doping boron into the carbon fibers. The two types of fibers examined in this study had dramatic differences in their respective microstructures and also in their overall reactivity. Relevant physical properties for both fibers are listed in Table 1. A brief description of each fiber follows. The P55 fiber is a mesophase pitch fiber which experienced a maximum heat treatment temperature of 2,773 K during its fabrication. It has a density of 2.04 g/cc and an outer diameter of 10.7 pm. The PAN T-300 fiber is a polyacrylonitrile fiber which experienced a maximum heat treatment temperature of 1,573 K during fabrication and also had a tensile load applied during fiber drawing and heat treatment to align the layer plane structure parallel to the fiber axis. It has an outer diameter of approximately 6 pm and a fiber density of 1.74 g/cc. Based on these data, the geometric surface area for the fibers were calculated.to be 0.18 mig and 0.37 mig for the P55 and T-300 fibers, respectively. Modifying the as-received (AR) fiber microstructure to inhibit oxidation and understanding the role of these modifications on the inhibition chemistry

Table 1. Physical properties of the as-received and reference carbon fibers Samples Properties P55 AR (VSB-32) Pitch 10.7 2.04 0.66 0.18 0.3430 2.218 0.040 8.16 P55 HT (VSB-32) Pitch 11.0 2.13 0.58 0.17 0.3400 2.237 0.022 4.69

T-300 AR PAN 6.2 1.74 0.56 0.37 0.35 2.173 0.115 20.01

T-300 HT PAN 5.8 1.88 0.59 0.37 0.3434 2.215 0.081 15.23

Type
Diameter, (pm) Density, (g/cc) Surface area,h (m/g) Geometric area,< (mig) d,,,,. nm X-ray density, (g/cc) Total pore volume, (cc/g) Total porosity, %

Based on density (p) gradient techniques.

Surface area determined by BET Kr absorption at 77 K. Calculated geometric area. dX-ray density = (0.33538/d,,) 2.268g/cc. Total pore volume = [ 1/p - l/x-ray p]. Total porosity = 100 x total pore volume.

Influence of boron on carbon fibers were the specific objectives of this work. Fiber modifications were accomplished either by heat treating or substitutionally doping with boron. 2.1.1 Reference fibers (Xl). Due to the large difference between the heat treatment temperatures of the AR PAN (1,573 K) and AR pitch (2,973 K) fibers, reference fibers (HT) were prepared. Samples of each AR fiber were heat treated to 2,773 K for 15 minutes under 203 KPa of Ar. The AR fibers heat treated in this manner are designated (HT). For the P55 pitch fibers this means that the HT sample has seen a temperature 200 K above the doping temperature. 2.1.2 Fibers doped with boron (B). In order to study the oxidation of the doped fibers, P.55 fibers were doped with elemental B so that the B/C atom ratio ranged between 4 x 10e5 (40 ppm B) and 5 x 10 (5% B). One boron loading of the PAN T-300 fiber was performed to give a 2 x 10. B/C atom ratio (2,000 ppm B)). 2.2 Boron doping process It has been previously established that the doping process used during the course of this study substitutionaIIy positions B atoms in the graphite crystal lattice[6-81. Fibers were placed in graphite crucibles and surrounded with an ultrapure flake graphite (SPl), which was coated with a boron-containing medium prior to packing the fibers. The boat was then sealed, placed in a graphite furnace, and heated at 2.773 K for 30 minutes under 203 KPa of Ar (ultrahigh purity, 99.99% Ar). The packing powder, a purified natural graphite powder. SP-1, was produced by the Union Carbide Corporation. SP-1 had an initial total surface area (BET, Kr. 77 K) of 1.8 m?ig and was guaranteed to have less than 1 ppm, total impurities. The use of a powdered medium was necessary because of the delicate nature of the fibers and the desire to dope uniformly. Powdered SP-1 was either coated with a liquid organoborane for dopings up to 1.000 ppm B or mixed with glassy B,03 for dopings above this level. 2.2.1 Preparation of the SP-1 Packing tedium. SP-1 was mixed with a known concentration of organoborane to achieve the B dopant level desired. The organoborane used throughout the course of this work was tributylborate-B(OCH,CHJJHzCH,),-manufactured by Fluka Chemicals. The purity level for this borane is >98%; it has a molecular weight of 230.16 g, a boiling point of 518 K, and a density of 0.875 g/cc at 293 K. At room temperature it is an oily liquid. In order to ensure a uniform distribution of the borane on the SP-1 surface, it was mixed with methanol and added to the SP-1 powder to make a slurry. This slurry was then mixed for 1.5 hours on a mechanical stirring plate, and the solvent was slowly removed by heating, leaving behind SP1 powder with a uniform borate surface coating. It should be noted that the concentrations of organo-

253

borane added to the slurry are higher than the final B dopant level in the fiber. This loss of B during doping was useful when trying to obtain very low (40 to 500 ppm) dopant levels. In the SP-1 batch used to dope the fibers containing 1,000 ppm B, it was not necessary to use methanol. T~butylborate was added directly to the SP- 1. It was mixed and dried slowly on a hot plate (to remove the organic fraction) until the SP-1 was again a dry powder. At this level organoborane addition, a uniform white coating was visible on the powder surface, indicating the presence of the borate. To achieve high B concentration levels (~2%). the liquid organoborane was substituted with glassy B,O, (99.999% purity, Aldrich Chemical Co., Inc.). Again, a specific concentration of the B,O, was ground, added to the SP-1, and mixed to obtain the 5% loadings. It should be noted that this material was a solid, and the process of slow drying was obviously not required. 2.2.2 Substitutional doping-heat treatment cycle. After coating the SP-1, it was distributed uniformly over the cut fiber sections in the graphic crucible, which was manufactured using ultrapure graphite (POCO-AXF 5Q). Once a crucible had been used to hold fibers doped to a specific concentration level, it was not used for dopings at lower B levels. The reason for this was simple. The amount of graphite in the crucible and lid far outweighed the relatively small amount of fiber and SP-1 packing. Once the crucible had been saturated with a specific concentration of B, there was little change in this concentration when heated with the fiber and SP- I. For the high-temperature heat treatments, the fibers were heated at 2,773 K for 30 minutes under 203 KPa of Ar (ultrahigh purity, 99.99% Ar) in a graphite tube resistance furnace. The crucible was placed in the center zone of the furnace, which was sealed and evacuated to 3.1 KPa. It was then pressurized to 23 KPa with UHP Ar. This process was repeated at least 3 times to ensure a negligible oxygen content within the furnace prior to heating. Argon was passed through the furnace at a rate of 100 ccimin, while maintaining the Ar pressure in the furnace at 203 KPa. This condition was maintained during the entire heat treatment cycle. An average heating rate of 293 Kimin was used to reach 2,773 K, at which the sample remained for 30 minutes, followed by a two hour cool-down cycle. Temperatures were monitored using a Leeds and Northrup Optical Pyrometer (Model 8636-C) calibrated against the melting points for Al,O, (2,345 K), TiB? (3,173 K), and MO (2.890 K). To avoid contamination of fibers during doping, an identical yet clean graphite tube was substituted for the original in which the caljbration was conducted. Any deviation in the temperature as a result of the substitution was thought to be small and to have little effect on the fiber preparation since the procedure for doping was consistent.

CAR

29:2-E

254 2.3 Fiber characterization

L. E. JONESand P. A. THROWER strumental broadening and when possible, for crystallite strain[9]. The average crystallite width, L,, can be measured from the widths of the (100) or (101) reflections. However, in most carbon fibers these peaks are weak and measurement is difficult. An empirical value can be calculated from the following formula[lO] using the measured interlayer spacing, d, but its applicability to these fibers is uncertain. d nm = 0.3354 + 0.059 L, 2.3.3 Surface analysis-Fourier transform infrared spectroscopy (FUR). Fourier transform infrared spectra of boron-treated fiber samples were obtained by adding 60 interferograms at a resolution of 2 cm-r using a Digilab FTS 60 spectrometer. The instrument was internally calibrated with a He-Ne Laser so that the frequency scale was accurate to within 0.2 cm-r. The advantage of an interferometer, as opposed to a system of slits and gratings, is that the interferometer allows greater optical throughput to the detector. An on-line microcomputer also makes it possible to curve resolve and to apply spectral methods. Fiber samples were prepared for FTIR analysis by combining 25 mg of KBr with a few flakes of fiber and ground for 30 seconds. This pregrinding technique was used on all samples. Additional KBr was added after pregrind to bring the total weight up to 275 mg, and this mixture was then ground for another 15 seconds. Total mixing time in the wigglebug (sample preparation cell) and transfer time to and from the pellet pressing apparatus had to be kept to a minimum to avoid excessive adsorption of HZO. The powdered mixture was then pressed and scanned immediately. Infrared spectra were then used to provide information on the nature of the fiber surface and the presence of a possible B,O, coating. 2.3.4 Microstructural observations-scanning electron microscopy (SEM). A scanning electron microscope equipped with an energy dispersive spectrometer was used to examine the surfaces of all selected fibers. Samples were coated with an Au conducting layer to minimize edge effects. All fiber samples were examined using accelerating voltages of either 5 or 10 kV. 2.3.5 Substitutionalpositioning of boron-magnetic susceptibility measurements. Magnetic susceptibility (x) measurements were carried out by the Faraday method using a modified Cahn RG electrobalance. Samples of the ultrahigh purity flake graphite (SPl), used as the packing medium during the doping process, were characterized using diamagnetic susceptibility before and after doping. Diamagnetic susceptibility measurements provide information on the overall electron population of the graphite. A pure crystalline graphite will have a diamagnetic susceptibility of -21.5 x 10m6emu/g along the layer plane dimension and -0.5 x 10m6 perpendicular to the layer plane. The presence of sub-

After doping with B, samples of each fiber along with the as-received (AR) fibers and the reference (HT) fibers were analyzed to assess fiber crystallite structure, elemental boron content, surface structure, and microstructural properties. Samples were also characterized on the basis of their rate of oxidation in pure 02, using a thermal gravimetric analyzer (TGA). The use of the TGA also provided samples for microstructural observations in the SEM after they were subjected to a low-level burn-off in O?. Due to the significance of the TGA in this study, its experimental procedures are described separately in section 2.4. 2.3.1 Elemental analysis-emission spectroscopy. Samples (0.02 mg) of each fiber specimen were submitted for trace elemental analysis. They were ground to less than 100 mesh size and analyzed using a Spectrametrics Spectraspan III, DC arc plasma emission spectrometer using standards containing known concentrations of B ranging from 100 to 5,000 ppm. Boron concentrations are reported as a ppm level or as a B/C atom ratio based upon the emission spectroscopy results. They are considered semiquantitative. 2.3.2 Crystallite properties-x-ray diffraction. Samples (0.05 g) of each fiber were ground in an agate mortar and pestle, sieved through a 100 mesh nylon screen, and mixed with 25 wt% pure silicon (NBS SRM 640) (Table 2) as an internal standard. After thorough mixing, a thin film of each sample was bound to a glass slide using collodion and examined using a Rigaku Geigerflex x-ray diffractometer with CuKa radiation. Peaks were obtained by scanning at 2 20imin with a time constant of 1 second. Slower scan rates were used to locate very weak diffraction peaks. Silicon was chosen as the reference material because its peak positions are close to those of graphite. Scans of each fiber were made between the angular ranges of 24-29, 41-48, and 53-57 and angular positions corrected using the standard Si peak positions. The interlayer spaceing (d) for each fiber was calculated using Braggs law, and crystallite sizes were calculated from the full peak widths at half their maximum height (FWHM) after correcting for in-

Table 2. Exact angular peak positions for Si SRM 640 and approximate positions for the major graphite peaks Silicon hkl 111 220 311 422 28 28.443 47.303 56.123 88.032 Graphite (ref. no. 23-64) 20 hkl 002 100 101 004 006 26.53 42.44 44.64 54.70 86.99

a = 0.543088 nm, A = 0.15406 nm, T = 298 K.

Influence of boron on carbon fibers boron in crystalline graphite will lower the Fermi level as a result of borons behavior as an electron acceptor. Substitutional boron will, in turn, cause the diamagnetic susceptibility of graphite to drop. This is the case only when boron is chemically bonded within the graphite structure. The diamagnetic susceptibility will not be lowered as a result of its presence in an interstitial site or as a surface oxide. Therefore, diamagnetic susceptibility is a technique with which to evaluate the location of boron in the graphite crystal structure. 2.3.6 Mechanicul properties. Fiber tensile strength and tensile modulus were determined at room temperature using a standard Instron frame with an LVDT (capacitance transducer) to measure displacement. Fibers were mounted to cardboard tabs using jewelers wax and were strained at 0.005 cmisec. Fibers were tested as individual filaments with gauge lengths of 10 cm. stitutional

25s

which the reactant gas (0,) was introduced and the experiment initiated. Rates obtained for the consumption of carbon in oxygen are expressed in terms of grams of carbon gasified per gram of remaining material per unit time (mg-carbon/mg,-hour).
3. RESULTS

2.4 Kinetic study of fiber oxidation-thermal gravimetric analysis (TGA) Fiber oxidation rates were measured and recorded using a Perkin-Elmer Thermogravimetric Analyzer (TGS-2. Thermal Analysis Data Station). Data were recorded as the percent initial weight loss per minute and were converted into percent burn-off versus time and to oxidation rates over specific time intervals using software. Data were normalized to the initial sample weight and to the instantaneous sample weight. In the experiments herein described, the initial sample weight was approximately 2.5 mg. Fiber samples cut to 3 mm lengths were placed inside Pt sample boats. They were oxidized isothermally in 0.1 MPa of dry ultra-high purity. hydrocarbon free O2 (> 99.99%, Linde Division of Union Carbide). Isothermal oxidations were conducted on each fiber at several temperatures between 923 and 1,073 K. Gas flow rates were maintained at 40 cc (STP)/min during each experimental run. Prior to the introduction of 02, samples were heated to the temperature of interest in 0.1 MPa of N2 (ultrahigh purity, >99.99%). Once the oxidation temperature was established, the sample was allowed to soak in N1 for approximately five minutes, after

3.1 Boron concentration in carbon fiber sumples The concentration of substitutional boron in the P55 fibers after heat treatment to 2,773 K increased with increased initial loadings of boron in the SP-1 packing. The smallest concentration was 4 x 10 B/C (40 ppm B). This sample is listed as P5S 40B in Table 3. The largest concentration was 0.05 B/C. which is listed as P55 5% B. In the T-300 fiber. only one boron doping level of 0.002 B/C was achieved. and this is listed as T-300 2,000 B. Magnetic susceptibility measurments made on the heat-treated SP-1 powder verified the sustitutional positioning of boron as a result of the processing. It was found that the total magnetic susceptibility (x) of the boron-doped SP-1 powder changed from an original value of -2.5 x lo- Cl emu/g to -0.25 x 10 emu/g. This change in x corresponds to a decrease in the Fermi level of the graphite, which occurs when boron atoms are present at trigonal sites in the lattice. This influence of boron on the diamagnetic susceptibility of graphite was first reported by Soule[6] and Delhaes and Marchand[ 111. McClure[ 121 independently derived a theoretical curve for the influence of boron on the Fermi level of graphite which was based upon his susceptibility theory. The Fermi level of single crystal graphite was shown to be 0.027 eV. The Fermi level begins to move into the valance band at a substitutional boron concentration of 1.4 x 10~ B/C and continues to decrease with increasing boron concentration. The behavior is due to the electronic structure of boron. The atomic radius of boron (0.098 nm) is approximately the same as that of carbon (O.OYl4 nm). and because boron is trivalent with a coplanar orbital structure identical to graphite, it enters the graphite lattice substitutionally at the trigonal sites[ 131. Boron is also electron deficient. having only three elec-

Table 3. Boron content of carbon fiber samoles Boron concentration. Emission Initial amount spectroscopy used to Dope SP-I analysis medium (ppm) tppm) NA NA 150 650 3,500 176,000 NA NA 3.500
10

ppm Value used (B/C atom ratio)

Sample

name

Fiber type P55 AR P55 HT P55 40 B P55 200 B P55 1.000 B P55 5% B T-300 AR T-300 HT T-300 2.000 B

IOU 40 200 I .ooo 50.000 30 30 2.000

111 i
2

4 x lo2 x IO

IO : 5 x I()~ 3 x 10 3 x IO 2 x IO i

256

L. E. JONESand P. A. THROWER

trons in its outer shell and, as a result, acts as an electron acceptor. Because of the substitutional nature of boron, the n-electrons between the layer planes are redistributed and the Fermi level is lowered due to this change in the number of available charge carriers[8,12]. The influence of electronic structure on the oxidation rate of graphite was first suggested by Long and Sykes in 1952[ 141. This is the theory of electron transfer by an impurity atom, and from this theory it can be argued that the activity of the carbon surface to chemisorb oxygen and subsequently desorb oxygen complexes (i.e., CO) is altered by the acceptance of electrons into the valance band of carbon. It is clear that the substitutional doping of boron into the graphite structure does far more than just serve to redistribute rr-electrons in carbon fibers, and the purpose of this paper is to identify these changes in the chemical and physical make-up of the fiber. A discussion of the influence of boron on fiber microstructure, physical and mechanical properties, as well as fiber reactivity follows. 3.2 Fiber x-ray crystallite parameters The fiber crystallite parameters of interlayer spacing, d, crystallite size, L,, and crystallite width, L,, are given in Table 4. Several boron doping levels were achieved in these fibers and, in general, the d spacing decreased with increasing boron content. The P55 fibers containing less than 200 ppm B, however, did not have a corresponding decrease in their d spacing. The x-ray crystallite parameters of the pitch fibers containing 40 and 200 ppm B remained relatively unchanged from those of the AR pitch fibers. Turnbull, Stagg, and Eeles in 1966 studied the substitutional solid solubility of boron in single crystal graphite[l5]. They produced a graphite containing as much as 4% boron and found that their materials containing high dopant levels (between 2 and 4% boron) had no systematic variations between the interlayer spacings and boron content. The boron concentrations which were found in each of these samples were a function of the heat treatment temperature experienced. Heat treatment of these boronated graphites also resulted in a change of the

Table 4. Carbon fiber x-ray crystallite parameters (nm) Fiber samples P55 P55 P55 P55 P55 P55 P55 AR HT 40 B 200 B 500 B 1,000 B 5% B d ooz 0.3430 0.3400 0.3427 0.3428 0.3422 0.3364 0.3356 0.3406 0.3500 0.3434 0.3350 0.3415 L 11 15 11 11 12 15 37 12 6 50 5 ~wnl, ~~(m,,

10 10

55

T-300 AR T-300 HT T-300 2,000 B

9 -

lattice parameters. The d spacings began to decrease from their original values at temperatures -1,470 K, and above 2,100 K began to increase toward the value of the interlayer spacing for a pure graphite. This result is due to the presence of boron in substitutional positions initially, which results in a contraction in the c dimension and an increase in the a dimension. As the concentration of boron doped into the lattice is increased, the substitutional solubility limit was reached and the boron atoms occupy interstitial sites, which led to the increase in the c dimension. This increase in d produced by boron at interstitial sites was greater than the contraction produced by substitutional boron atoms.The presence of interstitial atoms does not influence the a dimension. It was also found that by annealing to 1,700 K, interstitial boron diffuses out of the crystal. Substitutional boron atoms remain in their positions up to about 2,300 K. At this temperature or higher, boron is removed from its substitutional position by selfdiffusion, leaving behind vacancies which were observed as vacancy loops by transmission electron microscopy (TEM). Lowell[7] examined the solid solubility of boron in carbon over the temperature range 2,070 to 2,770 K and found the substitutional solid solubility limit to be 2.35 atomic % at 2,620 K. At higher temperatures the solubility did indeed decrease. The lattice parameters were found to be linear functions of the boron content with the c dimension decreasing and the a dimension increasing as the boron concentration increased. In the current study, we obtained significantly lower overall boron concentrations in both carbon fibers. The final boron concentrations achieved in the fiber were the result of changing the boron concentration in the packing medium or graphite boat prior to heat treatment. The temperature and duration of the heattreatment cycle were held constant during the course of the investigation. The influence of boron on the crystallite interlayer spacing, d, for both the PAN T-300 fiber and the pitch P55 fiber are given in Fig. 1. Substitutional boron in these fibers strongly decreased the interlayer spacings. In the P55 fiber the interlayer spacing approached that of a natural graphite (0.3354 nm) and leveled off at approximately 0.3356 nm at a boron concentration of -2,000 ppm. At this same boron concentration (-2,000 ppm), the interlayer spacing in the T-300 fiber was reduced to less than that of natural graphite. The sharp decrease in the d spacing for the P55 fiber occurred at roughly 500 ppm (5 X lo- B/C). At a 500 ppm boron level, some fraction of this fiber became more graphitic as a result of this increased boron content. The decrease in the interlayer spacing of the pitch fiber progressed steadily up to a boron concentration of 5%. At the highest achieved doping levels, the diffraction pattern of the pitch fiber had two distinct sets of graphite diffraction peaks resulting in two values for the d spacing for this fiber. Figure 2 is the modulated (002) diffraction peak for

Influence of boron on carbon fibers

257

E
G i= w c 2:

0.338

0.336

0.334

B /C

ATOM

RATIO

Fig. 1. Influence of the substitutional boron concentration on the interlayer spacing of pitch 855fiber 0 and PAN T-300 fiber A. At the higher doping levels two interlayer spacings were measured for PM and T-300 as indicated by 0 and 1, respectively.

the pitch fiber containing 5% boron. It is believed that the modulation of the diffraction profile for the highly doped pitch fiber is due to the presence of two distinct graphite fractions in the pitch fiber. It can be argued that these two distinct diffraction peaks arise from two different structures within the same fiber. The most intense peak results from a diffraction by the more ordered graphite fraction of the PSS fiber, (OOZ),;,while the less intense, more diffuse peak results from the turbostratic fraction of the PS5 fiber, (002),. The T-300 fiber also exhibited a similar behavior. The addition of boron to the T-300 fiber resulted in two distinct peaks at a doping level of 2,000 ppm B (Fig. 3). This is considerably less than the 5% level necessary for such a phenomenon in the P55 fiber. The ci spacing of the most intense T-300 2,000 B diffraction peak was 0.3350 nm, less than the interlayer spacing for a well-ordered pure graphite, 0.3354 nm. The second (002) diffraction peak for the T-300 2.000 B fiber was very diffuse and corresponded to a d spacing of 0.3415 nm. The smaller d spacing than that of pure graphite is supporting evidence for the substitutional positioning of boron in the fiber structure. All crystallite size, L,, measurements reflected the changes in both the P.55 and T-300 d spacings. The crystallite size generally increased with boron concentration. However, at the very low doping levels,

B/C ratios of 4 x lo- and 2 x lo-. the crystallite size remained constant. Low-level dopings with boron, up to 2 x 10ml Bi C, had little effect on the overall P55 fiber x-ray crystallite parameters. However, higher concentrations of boron in the P55 fiber (1,000 ppm B and 5%) altered the fiber structure by improving the crystallite alignment and size within the fiber. These carbon fibers with higher boron concentrations had lower oxidation rates because of the presence of boron. Mechanisms for oxidation inhibition are believed to be linked to the enhanced crystallite structure within these fibers. 3.3 Irlhibition ofcarbon fiber oxidation The presence of substitutional boron inhibited the oxidation of both of P55 and T-300 fibers; the degree of oxidation inhibition depended on the concentration and location of the boron present in the fiber. Burn-off versus time data for the AR, HT. and boron-doped P55 fiber samples at 973 K are given in Fig. 4. The presence of 1,000 ppm B reduced the oxidation rate by a factor of 6 at 973 K in 0.1 MPa ultra high purity 02. In general, the reduction in the reactivity of the PAN T-300 fiber was similar to that observed for the pitch P55 fiber but somewhat larger. Boron was a strong inhibitor of the PAN fiber-o, reaction. At a temperature of 973 K, the reaction rate decreased by a factor of 31.9 as a result of the

258

L. E. JONESand P. A. THROWER pitch fibers are presented where[ 161. more completely else-

3.4 Preferential oxidation of the carbon fiber microstructure Pitch and PAN carbon fibers were removed from the TGA after they had been oxidized to specific burn-off levels (i.e., 150/c, 50%, and 75%) and SEM micrographs were taken. During oxidation in 0.1 MPa of ultra high purity 0, over the temperature range of 923 to 1,023 K, the carbon fiber surfaces were oxidized preferentially at specific sites. In other words, accessible areas on the carbon fiber surface which had a high number of active carbon sites were selectively attacked by oxygen. It was believed that the noncrystalline portions of the carbon fiber contained the highest active surface area and for this reason were preferentially removed during the gasification process, revealing the well-ordered crystalline fraction of the carbon fiber. Obviously, the degree to which the crystalline microstructure was

NBS

Si

Standard

25

26

27 20

28

29

Fig. 2. Modulated (002) diffraction profile for the PS5 fiber containing 0.05 B/C atom ratio. NBS Si
Standard

addition of 2,000 ppm B (2 x 10s3 B/C) to the AR T-300 fiber (Fig. 5). Table 5 lists the reaction rates of the P55 and T-300 fibers as a function of boron concentration and temperature at 25% burn-off. Reaction rates are normalized to the weight of sample remaining. Note that an increase of ZOO K in heating temperature (HT versus doped) is approximately equal to a doping of 500 ppm. The P55 fiber containing 5% boron is not listed in Table 5 because it never reached 25% burn-off at the temperature of 973 K. The reactivity of this material was essentially zero after a 20% burn-off (seven hours of oxidation). Higher levels of burn-off (55% and 70%) were reached over much shorter periods of time (5.5 and 3 hours) at reaction temperatures of 1,023 and 1,073 K, respectively. This stopping of the fiber oxidation was also evident for the P55 fiber containing 1,000 ppm B and the T-300 fiber containing 2,000 ppm B. A 100% burn-off was not achieved for these materials over the temperature range studied. Details of the oxidation study of the

1
~._.....
24

(002 IT

i~__~~__--i
26 28 27 29

Fig. 3. Modulated (002) diffraction profile for the T-300 fiber containing 2 x 10m9 B/C atom ratio.

Influence of boron on carbon fibers

100
A.R. ., m-a 0 0 cl 200 B cl 0 0

0
HT cl 0 0 0 o 1000 B o

0 0 40<,

cl
0

o
o
P55 5%B

973 K

12

TIME, h
Fig. 4. Reactivity of the as-received (AR) and heat-treated (HT) PS5 pitch fiber and PSS fiber containing 2 x 10 1, IO-. and 0.05 B/C at 973 K in 0.1 MPa UHP 0,.

O:

AR &cl HT
0

l0 80--o ' ..n 0 60--o' '0 I, 00 40

Cl

cl
0

2000 B

0
0

u
T-300 973 K

:: : : ; ;:: : :5 ; ::: :1 :; : ::; 0-P:: 4 2 3 0

TIME, h
Fig. 5. Reactivity of the as-received (AR) and heat-treated (HT) PAN T-3011 fiber 2 x IO- B/C at 073 K in 0.1 MPa UHP O1.

and T-300 ~ont~~inin~

260

L. E. JONESand P. A. THROWER Table 5. Gasification rates normalized to remaining weight at 25% burn-off Rates (mgimg, hour) Samples P55 AR P55 40 B P55 200 B P55 1,000 B P55 HT T-300 AR T-300 HT T-300 2,000 B 1,023 K 973 K 1.96 1.74 1.11 0.33 0.43 10.20 2.92 0.32 948 K 1.15 0.93 0.41 0.21 0.25 923 K 0.54 0.34 0.19 873 K

0.82 1.35 0.83

4.76 0.74 0.06

2.15 0.32

revealed was a function of the level of carbon burnoff experienced by each fiber, as well as the concentration and orientation of the underlying crystalline microstructure. The microstructure and, hence, the location of preferential oxidation depended on the carbon fiber precursor, the maximum heat-treatment temperature experienced during the fiber processing, and the influence of the substitutional boron on the microstructure itself. These points can be seen in the next series of micrographs. Figure 6 is a micrograph of the unoxidized AR P55 fiber. This fiber had a uniform circular outer diameter and a textured inner core. This inner core appeared to have a random orientation of its microstructure; yet, as with many carbon fibers, ribbing was visible along the length of the outer fiber surface. Upon oxidation the inner core region was preferentially removed, leaving behind an outer fiber skin or sheath (Fig. 7). Substitutional doping of the AR P55 fiber with boron at all concentration levels retarded the preferential oxidation of the fiber core region. Oxidation of the P55 1,000 B fibers exposed a ribbon-like or fibrillar arrangement of the graphite crystallites after a 45% burn-off (Fig. 8). Instead of hollowing out the fiber core, as was the case with the AR pitch fiber, the fiber ends were tapered; attack by oxygen occurred at the outer fiber surface. Substitutional boron has enhanced the graphitization of the fiber core, which resulted in the development of crystallite ribbons parallel to the fiber axis. At higher boron concentrations (P55 5% B), the fibrillar structure was extremely rigidized. The contoured ribbons of crystallites seen in the P55 1,000 B fiber were no longer present (Fig. 9). The unoxidized AR PAN T-300 fiber had an irregular outer surface and an isotropic core (Fig. 10). The well-defined skin-core heterogeneity observed in the AR P55 fiber was not evident. Upon oxidation, all fiber surfaces, including the outer fiber surface, were oxidized (Fig. ll), and there are therefore no unique microstructural features. The AR T-300 fiber, however, which was oxidized to a low level of burn-off (15%), exhibited a concentric shell (circumferential) microstructure (Fig. 12). This structure is not a true onion skin (multilayer) structure as described by Donnet[l7]; however, it is a single zone

structure (no transverse heterogeneity), which is not true of the pitch fiber in this study. There are actually only two shells apparent in this structure, one which makes up the outer fiber surface and one in the inner core. This unique microstructure is observed, after low levels of oxidation, at the fiber e.nds, and deep grooves are visible along the fiber length. Preferential oxidation of the HT T-300 fiber resulted in a honeycomb structure when oxidized to -70% burn-off (Fig. 13). Removal of the more disordered fraction of this fiber during oxidation revealed a 3D ordering which occurred during graphitization at 2,973 K. This 3D honeycomb crystallite ordering in the HT T-300 fiber is unlike the commonly accepted ribbon model for carbon fibers previously observed for the oxidized P55 1,000 B fiber. A more appropriate 3D model proposed by Johnson et al.[18] described a structure in which wrapping and folding of crystallites encloses sharp-edged voids much like the structure in Fig. 13. This structural model proposed by Johnson et al.[lS] and Johnson and Tyson[l9] accounted for the turbostratic disorder which was believed to exist and was not modelled in the proposed carbon fiber ribbon structure. The basis for this model was their studies of graphitized PAN fibers using TEM in which they observed tilt and twist boundaries. Crystallites in PAN fibers were observed to be separated by intercrystallite boundaries and sharp-edged voids. Average crystallite widths were 6.5 nm, and voids were roughly 1 nm across. The model depicted an unstable turbostratic form of the crystallites in a carbon fiber which were believed to be restructured during graphitization as a result of a growth in the c dimension and a straightening out (untwisting) and growth of the a dimension. It is clear from the diffraction data that the c dimension of the PAN fiber does grow during graphitization and ordering occurs; however, there is no evidence for the growth of the a dimension. Figure 13 seems to indicate that a considerable amount of disorder exists along the a dimension and that it remains twisted as described by the turbostratic model. Oxidation of the T-300 2000 B fiber revealed no attack of the outer fiber surface; however, the fiber ends were preferentially oxidized (Fig. 14). Examination of the ends of fibers oxidized to a burn-off

Influence of boron on carbon fibers

Fig. 6. As-received pitch P55 fiber

Fig. 8. P55 fiber containing lo- B/C oxidized to a 45% burn-off in 0.1 MPa UHP O1.

of 35%~ exposed a cross-linked network of crystalhtes similar to that previously seen in the HT T-300 fiber. Further oxidation of this fiber to burn-offs of 70% or greater yielded droplets of boron oxide on the fiber surface (Fig. 15). This oxide accumulated on the fiber surface at the specific sites of preferential oxygen attack (i.e.. where oxidation removed carbon from the structure and exposed a substitutional boron atom, which then chemisorbed oxygen and prevented further carbon consumption at that site). This is the mechanism of specific site blockage and is one of several mechanisms operative during the inhibition of carbon oxidation by substitutional boron(l61. 3.5 The effect of boron on carbon fiber mechanical properties Table 6 lists mechanical properties for selected pitch fiber samples. Thus far, we have shown that boron strongly influenced graphitization and, hence, the structural properties of the carbon fibers. From these mechanical data it is clear that the addition of boron degrades to some extent both the fiber strength and modulus. The decrease in the strength and modulus roughly corresponds to the lowering of the crystallite interlayer spacing (Fig. 1). It is unclear why these properties drop off since boron enhances graphitization and, thus, aligns crystallite planes along the fiber axis. A previous study by Mayer. Cooper, and Allen[20] on the influence of boron on PAN

fiber mechanical properties found a significant increase in both the Youngs modulus and tensile strength with the addition of substitutional boron. More work is needed in this area to further clarify the influence of boron.
4. DISCUSSION

4. I Mechanisms of carbon fiber oxidation inhibition by substitutional boron There are actually three mechanisms involved in the inhibition of the carbon fiber oxidation via substitutionally doped boron. These mechanisms are described in detail elsewhere[l6] and are summarized here for clarity. The first mechanism, that of specific site blockage, is the controlling inhibition mechanism when large loadings of substitutional boron are present. As the oxidation of the fiber progresses, a barrier layer of boron oxide develops on the surface and caps off specific surface active sites, impeding the diffusion of oxygen to the graphite and slowing any further oxidation. This process could be seen in its advanced stages in Fig. 15, but it is an operative mechanism at any stage in the reaction when a specific active site is attacked and boron is exposed. Figures 16a and 16b are FT-IR spectra of oxidized AR PSS and P55 1.000 B fibers. respectively. Upon oxidation,

Fig. 7. P55 fiber oxidized to a 70% burn-off in 0.1 MPa UHP OZ.
CAR

Fig. Y. PS5 fiber containing 0.05 B/C oxidized to a 50% burn-off in 0.1 MPa UHP 0,.

29:

2-F

262

L. E. JONES and P. A. THROWER

Fig. 10. As-received PAN T-300 fiber.

Fig. 12. As-received PAN T-300 fiber oxidized to a 15% burn-off in 0.1 MPa UHP OS.

the AR samples exhibited a characteristic carbonyl spectrum. The most intense peaks for this carbonyl compound were: strong C==O stretch at 1,718 cm-, medium acid O-H stretching vibrations (bonded) between 2,980 and 2,950 cm-, and O-H bending between 1,110 and 1,030 cm-. These bands coupled with an intense band near 1,400 cm- are indicative of carboxylic acid (R-C-OH) groups on the AR pitch fiber surface (Fig. 16a). As a result of boron addition to the P55 fibers and subsequent oxidation, the surfacs of these fibers change. Eventually, a level of carbon fiber oxidation is reached at which the reaction stops. This is due to boron accumulation on the surface, which quickly forms an oxide coating which inhibits further oxidation. The characteristic FT-IR bands for this coating were: a strong B-OH stretch at 3,228 cm-, a strong B-O stretch at 1,446 cm-, and several weak B-O deformation bands between 1,200 cm- and 800 cm- (Fig. 16b). A boron oxide protection layer is formed only at sites subjected to oxidation, and thus this mechanism is termed specific site blockage. The second mechanism of fiber oxidation inhibition is chemical inhibition via electron transfer. As described previously, the activity of the carbon active surface sites is reduced due to the presence of substitutional boron in the internal lattice structure. Boron present substitutionally alters the distribution of T-electrons and, as a result, slows the desorption

of -CO, which is considered the rate controlling step of the C-O, reaction. Oxidation inhibition controlled solely by electron transfer was observed for fibers doped with 200 ppm boron or less. This chemically controlled oxidation inhibition mechanism is supported by a large increase in the activation energy for the C fiber-o, reaction which was observed for fibers with low boron levels. Finally, the third oxidation inhibition mechanism is due to the development of the fiber structure as catalyzed through the addition of boron. Carbon fibers become more graphitic as the layer planes become more ordered and the crystallite dimensions increase. This typically results in a decrease in the total number of accessible active surface sites (e.g., area) and, hence, results in a decrease in the reactivity of the fiber. At issue is how and where is boron the most effective inhibitor of carbon oxidation when it is chemically bound to (subtitutional doped into) the hexagonal graphite lattice structure. 4.2 Carbon fiber structure: The influence of substitutional boron It has previously been established that boron is preferentially doped into disordered or turbostratic carbon materials, as opposed to graphites with a high degree of crystallite orientation[21]. Boron also induces graphitization in these fibers. The influence

Fig. 11. As-received PAN T-300 fiber oxidized to a 70% burn-off in 0.1 MPa UHP 0,.

Fig. 13. Honeycomb structure of the heat-treated T-300 fiber oxidized to a 70% burn-off in 0.1 MPa UHP 0,.

Influence of boron on carbon fibers

263

Fig. 14. Preferential oxidation of the end of a PAN T-300 fiber containing 2 x 10 ~B/C after burn-off of 35% in 0.1 MPa UHP 0:.

of substitutional doping on carbon fiber graphitization was shown in Fig. 1. The location and influence of boron on each of these fiber structures is clearly unique and a function of the fiber precursor and the processing cycle experienced by each fiber. A more detailed description of the role of boron in dictating carbon fiber structure is given here. 4.2.1 Boron as a gruphitization catalyst in carbon fibers. The AR pitch fiber is more graphitic than the AR PAN fiber; yet, as with most carbon materials, both fibers contain small regions in which the carbon atoms are arranged in a graphite layer structure and large regions where defects and disorder predominate. Upon heat treatment, some reordering of these layer planes occurs; the graphite crystallites grow and the layer plane stacking order improves. The end result is a material containing a large amount of the stable hexagonal form of graphite. Graphitization, for this reason, can be said to be the process of developing a three-dimensional structural order in the carbon material through the progressive removal of defects within and between the graphite layer planes. Boron accelerates the graphitization process. The catalytic behavior of boron on the graphitization process is controlled by the thermally activated mechanism of carbon self-diffusion. Structural defects in

carbon are removed and distortions are relaxed as a result of heat treating to temperatures in excess of 2,473 K. Graphitization is often described as a two-stage process in which self-diffusion via interstitial migration is considered the mechanism of the first stage. Self-diffusion results in the ordering of layer planes and an increase in the layer plane stacking dimension, L,.The second stage of graphitization involves the lateral growth of crystallites during which a concomitant growth of L, and L, occurs.The activation energy, E,, value for B diffusion in carbon is roughly the same as the E, for self-diffusion, -6.8 eV. The influence of boron on the graphitization process is dictated by the diffusion constant for boron and not by the diffusion activation energy. Hennig[22] found that at temperature between 1.970 and 2,760 K the diffusion constant for boron migration in the a direction (6,320 cmis) is much greater than that in the c direction (7.1 cmis). The mobility of boron within the structure was also found to be relatively insensitive to the boron concentration for the B/C range between 10 z and lo-. Diffusion constants for carbon migration are considerably lower than those for boron. Using a C tracer, the selfdiffusion constants were found to be 82.8 cm?!s and 1.82 cmis in the II and c directions, respectively[23]. These findings substantiate the belief that B and C diffuse in the lattice structure in an identical manner and that the graphitization process is accelerated through a mechanism which is enhanced by an amount comparable to the increased diffusivity of boron over carbon atoms in the lattice. The effects of B on the crystallite interlayer spacing, d. for both the PAN T-300 fiber and the pitch P55 fiber are given in Fig. 1. It has been argued that as a result of its atomic size, substitutional boron increases the a lattice parameter and decreases the c parameter[7]. This size argument alone is not enough to explain the reduction in the c lattice parameter (d spacing) given in Fig. 1. The presence of substitutional boron in these carbon fibers strongly reduces the value of the interlayer spacing, d,,,,,. Graphitization. shown by a reduction in the interlayer spacing, is enhanced by substitutional boron at concentrations greater than 2 x 10 B/C in the PS.5 fiber. The influence of boron on the crystallite width is not as dramatic. The crystallite width or diameter, L,,, can be determined using line widths of the diffraction profiles of the (100) and (101) planes in
Table 6. The influence of substitutional mechanical properties Tensile strength (ksi) 275 182 180 134 boron on

Fibers P55 P55 200B P55 SOOB P55 5% B

Tensile modulus (Msi) 55 so 47 27

Fig. IS. Droplets of oxide on the surface of the PAN T300 fiber containing 2 x lo- B/C after oxidation to a 70% burn-off in 0.1 MPa UHP Oz.

L. E. JONESand P. A. THROWER
P55AR I 1 I

3800

3000

2000
WAVENUMBERS

1000

450

Fig. 16~1.FT-IR spectrum of the oxidized sm-face of the as-received P55 fiber.

P55

3800

3000

2000
WAVE NUMBERS

IO00

450

Fig. 16b. FT-IR spectrum of the oxidized surface of the P55 fiber co~ta~~i~g lo- BIG

Influence of boron on carbon fibers graphite. Figure 17 defines these dimensions in a graphite crystallite. The crystallite parameter, L (101) (as measured by the breadth of the (101) peak), is as much an L, dimension as an L, dimension since it cuts obliquely through the thickness of the crystal. In this sense, it is a true measurement of the degree of 3D order of the graphite crystals in these carbon fibers. The L, dimension may indeed grow, yet the L,( 101) dimension will remain the same if the ABAB . . stacking sequence is periodically interrupted by crystallite twist boundaries. The L parameter calculated from the line width of the (101) peak is an indication of the regular development of three-dimensional order within the fiber. in the carbon fibers studied, both L,, and L,(101) are not affected by the increase in the boron concentration up to a 5% boron doping level (Table 4). It can. therefore. be argued that since these values are not growing with respect to the increased ~~rn(~unt of subsitutional boron. the graphitizati~)n process in carbon fibers is accelerated by an increase in the first stage of graphitization (diffusion via interstitial migration to eliminate defects), which is a result of the increase in the rate of boron diffusion into the fiber structure. At a boron concentration of 10 B/C in the P55 fiber (PSS 1.000 B), the d spacing dropped to 0.3364

XI5

nm (Fig. 1). The n spacing for perfect graphite is 0.3354 nm. Pitch fiber P55 1,000 B was not entirely graphitic as a result of boron doping. The d spacing of the P55 1,000 B decreased by 0.0066 nm from the d spacing of the AR P5.5 fiber. A further increase in the P55 fiber boron concentration, to a level of 5% B, decreased the d spacing by an additional 0.008 nm, which is only a slight improvement in the crystallinity of the material as a result of a 50-fold increase in the boron concentration. However. it is fairly certain that not all of the boron in P55 5% is present substitutionally. The d spacing for the T-300 fiber doped with boron (T-300 2.000 B) does fall below the d spacing fat perfect graphite. This concentration level (2 x 10 B/C) is far below the 2.35 atom % soiubiiity limit for boron in carbon. The graphitization of the PAN T-300 fiber is also enhanced by the presence of suhstitutional boron. This very low d spacing value for the PAN fibers containing boron supports the presence of boron substitutionally in this fibers structure. 4.2.2 Crystallite length. L,,, in boron-dopeci fi'her.s. Bending of the crystallite layer planes was observed in the P5.5 1,000 B fiber (Fig. 8). In this micrograph, the skeleton of the P55 1,000 B fiber was exposed upon oxidation in 0.1 MPa of UHP 0,. This skeleton

Twist .Boundary

Fig.

17. Crystallite

dimensions

in an ordered

graphite

crystal

266

L. E. JONES and P. A. THROWER react or fuse with other carbon fibers. Unsaturated side groups present in the linear molecules of polyacrylonitrile can cause additional polymerization reactions. To avoid this, PAN fibers are heated in a controlled oxidizing atmosphere -500 K under tension for several hours. As a result, several thermally activated processes occur which cause a reorganization of the polymer chains and three-dimensional linking of parallel molecular chains by oxygen bonds. These oxygen cross-links keep the chains straight and oriented parallel to the fiber axis even after the release of tension following the stabilization process. Cross-linking between chains of PAN prevents true ribbons of crystallites from forming. Instead, a honeycomb crystallite backbone enveloping box-like porosity was produced during heat treatment. Diffraction by the (100) and (101) planes of the heattreated T-300 fibers did occur; however, these reflections were lost upon the addition of boron. The influence of substitutional boron on the L,, (100) dimension for the PAN fiber (T-300 2,000 B) resulted in the loss of the (100) reflection. It is possible that because the presence of substitutional boron has forced this fiber d spacing to be below that of graphite, some break-up and shortening of the a dimension occurred and tilt bounda~es were formed between these crystallites. Substitutional boron, which catalyzes the first stage of graphitization, does bring the layer planes closer together and increases L,; however, boron also disrupts the L, dimension and creates an increase in the number of tilt boundaries, which results in the loss of the (100) reflection for the T-300 2,000 B fiber. 4.2.3 ~odulut~o~ of the (006) resection by substitutional boron. Modulation of the (002) diffraction profile of the P55 fiber occurred at a 5% B doping level (Fig. 2). Modulation of the PAN T-300 (002) diffraction profile occurred at a much lower boron concentration of 2,000 ppm B (Fig. 3). Modulation was noticed as a slight shoulder on the (002) profile of the P55 fiber containing 1,000 ppm B. It is believed that in these modulated diffraction profiles, the most intense peak results from diffraction by the more graphitic fraction of the fiber, while the less intense and broader peak results from diffraction by the more disordered (turbostratic) fraction of the same fiber. The crystallite size, L,, of the graphitic fraction of P55 5% B is 40 nm. The L, value for the turbostratic fraction of the same fiber is 12 nm. An explanation for these different structures is centered around the presence of substitutional boron, where influence on the structure, oxidation resistance, and physical properties of the fiber cannot be associated with a homogeneous distribution of boron throughout the structure. This variation in boron concentration is, as evidenced by SIMS anaiysis of boron-doped pyrolytic graphite[21], due to a larger boron uptake by that portion of the fibers structure which was originally amorphous or turbostratic as opposed to crystalline (graphitic). Be-

is actually a series of undulating ribbons of crystallites oriented parallel to the fiber axis. This ribbon structure was first described by Watt and Johnson in 1969f24j and is shown schematically in Fig. 18. The proposed structure was one in which ribbons of crystallites were aligned parallel to the fiber axis. The average width of the ribbons was about 10 nm, which was reported as the L, value. The crystallite length, L,, was only 6-12 nm. These small crystallite lengths are indicative of a turbostratic arrangement of crystallites in the a dimension. The irregular contours of these ribbons created voids which were long and narrow, or slit-shaped. These slit-shaped voids had cross-sections no greater than l-2 nm and lengths 20-30 nm. The measured L, (based upon the (100) peak width) for these fibers was only 10 nm. Increasing the boron content in the P55 fiber to 5% rigidized the P55 fiber structures. The layer planes have a needle-like appearance (Fig. 9) which is in strong contrast to the ribbons of crystallites found in the P55 1,000 B fiber. There was no bending of the layer planes in the P55 5% B fiber, and as a result, well-defined (100) and (101) reflections are observed. The HT T-300 structure as revealed via low-level gasi~cation was a honeycomb network of crystallites (Fig. 13). A considerable amount. of cross-linking existed between the crystallite layer planes. Crosslinking of the PAN fiber structure is a residual feature of the oxidation-stabilization step during processing. Once the fiber is stabilized, it is unable to

I--.---20H-I
Fig. 18. Ribbon structure of the graphite lattice in a highmodulus carbon fiber, from Fourdeux et al. [25].

Influence of boron on carbon fibers Table 7. Boron contents of the progressively oriented pyrolytic graphites analyzed using SIMS

267

d spacing.
Sample LOPG HTPG HPPG nm 0.3423 0.3400 0.3376

Boron concentration. after doping

ppm

Values used

(B/C) atom ratio

cause of this, its structure and properties are significantly more enhanced. To verify that boron is preferentially doped into disordered material, three pyrolytic graphites of different perfections were doped simultaneously with 1,500 ppm boron under conditions identical to those used to dope the carbon fibers. Each of these graphites was evaluated for crystallite parameters and uptake of elemental boron. The least oriented of the pyrolytic graphite samples (LOPG) was an as-deposited sample. Next was a slightly more oriented sample, a pyrolytic graphite which was deposited and subsequently heat treated to 2,973 K (HTPG). The third sample was a hot-pressed highly oriented pyrolytic graphite (HOPG) which possessed the highest degree of crystallite development and preferred orientation of the samples investigated. Table 7 lists these samples, their intertayer spacings, and their boron contents as measured using SIMS. As shown, the amount of boron doped into these samples decreased with increasing degree of crystallite orientation (graphitization). The most disordered sample, LOPG. had double the boron concentration found in the most graphitic sampte, HOPG, even though the initial boron concentrations used to dope these materials were identical. No boron concentration gradient through the specimens was observed. As described, the microstructure of each of the as-received carbon fibers is inhomogeneous. Specific fractions of the AR fiber are quite graphitic, whereas other fractions of the very same fiber are turbostratic. An example of this type of structural inhomogeneity is the AR pitch fiber structure, which has a graphite outer sheathing and an internal amorphous core. Upon oxidation the core region preferentially oxidizes. leaving behind a hollow graphite skin. Because the internal core of this pitch fiber has a considerably more random structure than the basal graphite outer fiber surface. or skin, it takes up substantially more elemental boron than the outer surface region. The take-up of substitutional boron enhances graphitization and the development of the skeletal or inherent substructure of the fiber. The graphite fiber outer skin also takes up substitutional boron, but because of its already ordered and welloriented microstructure, it takes up a lower concentration of boron than the disordered core region. Boron substitutionally doped into both these structural regions catalyzes graphitization and enhances

the crystallite structure within the core region preferentially over the fiber outer sheathing. The degree to which the crystal structure is enhanced in both regions is a function of the substitutional boron concentration and the original degree of microstructural order. Hence, we observe the modulated diffraction profiles of these two graphite fractions within the same fiber. Upon oxidation, the more graphitic region of the fiber, designated (002),, on the modulated diffraction peak, is attacked preferentially over the less ordered graphite region, designated (002)r. Figures 19 and 20 are the (002) diffraction profiles for the P55 1.000

24

25

26 28

27

28

Fig. 19, The (002) diffraction profile for the oxidized P5S fiber containing 10 B/C. The graphite fraction of this fiber is preferentially oxidized; the only diffraction peak which remains is that of the turbostatic fraction.

268

L.E. JONESandP A. THROWER

the inherent 3D cross-linked substructure of the fiber which develops during boron doping. This 3D substructure is also protected during oxidation by the formation of an oxide barrier layer. 5. CONCLUSION The AR P55 fiber contains a strong skin core heterogeneity in which the outer fiber skin is considerably more graphitic than the fiber core. Upon oxidation, the fiber turbostratic core region oxidizes preferentially. This oxidation behavior reverses itself upon the addition of substitutional boron. The reason for this change in behavior is a result of the location and concentration of boron in the fiber. Boron is preferentially doped into the disordered P55 fiber core. The concentration of boron substituted in the fiber is proportional to the number of defects which exist in specific regions or zones of the fiber structure. As a result, there is a higher concentration of boron in the turbostratic core region than in the graphitic fiber skin. The addition of boron results in the ordering of both of these structural regions in the fiber; however, the oxidation protection of the fiber is not provided by an increase in crystallite order but by the mechanism of specific site blockage. The fiber core contains more boron than the fiber outer skin and can, therefore, form an oxide layer more readily. It is also believed that the order in the fiber core region does not approach that of the fiber skin. All carbon fibers maintain their original structural nature (orientation) as dictated by their precursor and processing histories; only the crystallite order is enhanced through heat treating and/or boron doping. The same processes are operative in the PAN T-300 fiber; however, there is not as clear a structural gradient in the PAN fiber. The 3D cross-linking structure observed throughout the oxidized HT PAN T-300 is an inherent part of the original fiber structure. The degree of crystalline order of the 3D cross-linked microstructure is enhanced through heat treatment. This 3D cross-linked microstructure may itself act as a reinforcement in the PAN fiber. Since it is not present as a gradient microstructural feature, this 3D network in the fiber may result in the enhanced mechanical behavior shown by Mayer, Cooper, and Allen[20]. A gradient microstructure exists in the P55 fiber and is observed as the skin/core regions previously described. These regions are further delineated through heat treatments and boron doping. This nonuniformity in fiber structure gives rise to stress concentration at the interface between the fiber skin and core, which results in the observed decrease in fiber mechanical properties as a result of boron doping.
REFERENCES 1. D. W. McKee, C. L. Spiro, and E. J. Lamby, Carbon 22, 507 (1984). 2. D. W. McKee, Carbon 24, 737 (1986).

25

26 29

27

Fig. 20. The (002) diffraction profile for the oxidized PAN T-300 fiber containing 2 x IO- B/C; only the turbostatic fraction of this fiber remains after oxidation.

B and T-300 2,000 B fibers, respectively, after they were oxidized to a 30% burn-off. Only the (002), profile remains after oxidation for both fibers. The most graphitic fraction of the fiber, {002),, is preferentially removed. The fraction of the fiber yielding the (002), reflection contains significantly more substitutional boron after doping and, hence, is more easily protected than the graphite fiber fraction when exposed to oxygen at high temperatures. Upon exposure to oxygen, the boron which is located at specific surface active sites becomes an oxide, thus forming a protective barrier preventing further oxidation of the carbon substructure. Micrographs of the boron-doped pitch P55 fiber (Fig. 8) exhibit ribbons of crystallites running the length of the fiber. There is no longer an outer fiber skin in the oxidized specimen, even though it was originally clear that the fiber skin was considerably more graphitic than the pitch fiber core in the AR fiber. The pitch fiber skin is preferentially oxidized in the boron-doped samples because it contains less boron than does the core region. Oxidation of the fiber core is no longer evident. The ribbons of fiber crystallites developed in the region which was originally the random or turbostratic fiber core are the inherent fiber substructure, which is protected from oxidation as a result of the higher doped boron concentration and the subsequent formation of a boron oxide protective layer. The same argument holds for the PAN T-300 fiber, although this AR fiber contains a significantly lower concentration of ordered structure originally. The (002)r reflection given in Fig. 20 is also produced by

Influence 3. J. R. Strife
369 (198X).

of boron
67,

on carbon

fibers

269

and J. E. Sheehan. P. A. Thrower,

Ceramic

Bulletin

4. L. E. Jones.
Carbon (1970).

and P. L. Walker, Jr.,

Carbon

Jr.,
8, 375

24, 51 (1986).

5. D. J. Allardice

and P. L. Walker.

0. D. E. Soule, Proc. Fifth Conf. on Carbon, Pergamon Press, Elmsford. NY, 1, 13 (1962). 7. C. E. Lowell, J. Amer. Cer. Sot. 50 (3). 142 (1967). x P. S. Grosewald and P. L. Walker. Jr., Tanso 61, 52
(1970).

9 P. A. Thrower IO H. Akamatu.
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