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JOURNAL OF MATERIALS SCIENCE 17 ( 1 9 8 2 ) 309--322

Review
Phenomena of catalytic graphitization
A. O Y A
Faculty of Technology, Gunma University, Kiryu, Gunma 376, Japan
H. MA R S H
Northern Carbon Research Laboratories, School of Chemistry, University of
Newcastle upon Tyne, Newcastle upon Tyne, UI~

In recent years the phenomena of catalytic graphitization have developed considerably.


Four types of catalytic graphitization are known to produce G-, Ts-, A- and Tn-
components. The review summarizes the use of elements, alloys and compounds as
catalysts. The importance of catalyst particle size is stressed as well as the method of
addition of the catalyst to the carbon. Extents of graphitization induced by catalysts
are markedly dependent upon the existing degree of graphitization already present in the
parent carbon. The effects of graphitization at different temperatures are summarized
as well as the effects caused by the ambient atmosphere, for example by oxygen and
nitrogen. Mechanisms of catalytic graphitization resulting in G-, T s-, A- and Tn-
components are outlined and changes in synthetic graphites caused by catalytic graphi-
tization are presented.

1. Introduction and wood, do not graphitize on heat treatment to


Graphites are materials of significant importance graphitizing temperatures.
to a technological society [1]. Their high electrical Graphite is made commercially by electrical
conductivity, combined with their thermal and resistive heating (to temperatures in excess of
chemical resistance, enables them to be used as 3300K) [1] which process forms a significant
electrodes in steel making, as electrodes in the proportion of the total manufacturing costs. Any
chemical industry, as refractory materials in progress towards being able to make an acceptable
chemical and high-temperature applications and graphite at temperatures below 3300 K is there-
in nuclear reactors [2]. fore of great interest. The phenomenon "catalytic
Fig. 1 is a diagrammatic representation, showing graphitization" is well established since the inven-
stacking sequences, of constituent lamellar mole- tions of Acheson [4]. Industrially, catalytic
cules, in isotropic, graphitizable, turbostratic and graphitization does not have extensive applications
graphitic (graphite) carbons. The crystallographic because of the undesirable characteristics of
order, already present in graphitizable carbons graphites containing significant amounts of residual
of heat-treatment temperature (HTT) 700 to catalyst material.
1300K, is established as the lamellar nematic Several reviews of catalytic graphitization are
liquid crystals and mesophase of the carbonization available [5-8]. Traditionally, catalytic graphi-
process [3]. It is the approximately parallel tization refers to the enhancement of the crystal-
stacking sequences of molecules in the initiating linity of the carbon by the formation of graphitic
liquid crystal which is perfected towards hexa- material involving a chemical reaction between
gonal graphite at graphitization temperatures. the ungraphitized carbon and the metal or in-
Some carbons, usually isotropic (see Fig. la.) organic compound which constitutes the graphi-
and prepared from parent materials which do not tization catalyst. Recently, this rather limited
fuse, for example from thermosetting resin, copra view of catalytic graphitization has been extended
0022-2461 ]82/020309-1453.40/0 9 1982 Chapman and Hall Ltd. 309
(a) I$otropic carbon (b) Graphitizable carbon

0
.t_
t ' .b

0 I
,

(c) Turbostratic carbon

0.142 nm

o--- ic---o~

(d) Graphitic carbon

Figure I Diagrams of structures of (a) isotropic, (b) graphitizable (c) turbostratic and (d) graphitic carbons.

using new experimental techniques. This review years, mainly by workers in Japan and Germany.
summarizes the established aspects of catalytic The phenomena of catalytic graphitization are
graphitization and outlines these new catalytic now known to be extensive and complicated.
effects. This review attempts to place these phenomena
into four categories or processes and sets out
2. P h e n o m e n a o f catalytic graphitization methods of catalytic graphitization, of resultant
The processes of the catalytic graphitization of structures and properties as well as considering
carbon have been studied extensively in recent industrial implications.
310
Figure 2 X-ray diffraction (0 0 2)
(a) G-effect (b) Ts-effect profiles of carbon before (dotted
line) and after (solid line) catalytic
graphitization.

L~I , I, I ,I , I, I , I , I I , I , I ~ I t I i I J I t I i I
22 24 26 28 30 22 24 26 28 30
ZO(CuKr176 Z0(CuKa) (0)
(d) Tn-effect

I , I i I ~ I ~ I i I J I , I i I

22 24 26 28 30 22 24 26 28 30
ZO(CuKa) (o1 ZO{CuKa) (~

2.1. The G-effect 2.3. The A-effect


Graphitic carbon (the G-component, Fig. ld), A more homogeneous catalytic graphitization
with a doo2-spacing of approximately 335.4 pm can occur if the parent carbon is heated with a
and a crystalllte height, L e > 50 nm can form very finely divided catalyst such as vaporized
within a less-crystallhle parent carbon on heating metal or by elemental substitution in the carbon
with a graphitization catalyst which is usually crystallite. Fig. 2c shows the single sharpened
present in appreciable quantity. The X-ray diffrac- profile of the doe2 diffraction resulting from so
tion pattern of such graphJtized material is a treating a phenolic resin carbon. A phase-contrast
composite of a broad profile from the parent micrograph of this A-component is shown in
carbon and a sharp profile from the G-component Fig. 3c [16].
(20 = 26.5~ see Fig. 2a. This is a multi-phase or
heterogeneous graphitization. Graphite which 2.4. The rn-effect
is found in cast iron [9] or kish graphite of the A non-graphitizing carbon heated to graphitization
iron melt [10] is of this type. Fig. 3a shows a temperatures gives a complicated ( 0 0 2 ) X-ray
high-resolution phase-contrast transmission elec- diffraction profile in which a broad profile has,
tron micrograph of fringehmages from the lattice superimposed over it, two small but sharp peaks
of a G-component graphite. situated at 26 ~ (Tn-component) and 26.5 ~ (G-
component) [18-21]. If a non-graphitizing
2.2. T h e T s - e f f e c t carbon is heated with a suitable catalyst, for
If the catalyst is finely divided (e.g. 20 nm nickel example charcoal with calcium vapour, the peak
particles) and heated with a non-graphitizing of the Tn-component becomes quite pronounced
parent carbon the more ordered, turbostratic T s- at a temperature above 1700 K, see Fig. 2d. This
component (not the three-dimensionally ordered Tn-component, with a doe2 of 342.8 pm and Le
graphitic structure, Fig. l c) is formed. Values of of 90 nm [22, 23], is turbostratic, as is the Ts-
doe2 and L c vary from 338 to 342 pm and from component, and shows interference bands at
6 to 20nm, respectively, dependent upon the intervals of 20 to 30 layers. A sharp peak situated
catalyst used and calculated from the broadened at 26 ~ becomes pronounced also on grinding a
profile at around 20 = 26 ~ using CuKa. This non-graphitizing carbon [24], but it is not known
turbostratic structure is stable and remains un- if this component gives interference bands of the
changed on heating to 3 3 0 0 K at a pressure of type seen in Fig. 2d.
0.1MPa [11,12] or to 2300K at 0.5 GPa [13~.
Fig. 2b is the composite X-ray diffraction profile 3. Conditions of catalytic graphitization
of the parent carbon and Ts-component (20 = 3.1. Elements of catalysts
"-" 26~ A phase-contrast micrograph of the T s- Ishikawa and co-workers [25,26] attempted
component is shown in Fig. 3b [14-17]. unsuccessfully to categorize the efficiency of
311
Figure 3 High-resolution phase-contrast electron rnicrographs of: (a) the G-component, PF carbon, 30 wt% Ni, with
HTT of 2100 K, 0 min soak [16] ; (b) the Ts-component, PF carbon, 1 wt% Ni, with HTT of 1700 K, 0 min soak [16] ;
(c) the A-component, PF carbon, no additive, with HTT of 2100 K, 1 h soak [16] ; (d) the Tn-component, charcoal
catalyzed by calcium vapour, with HTT of 2100 K, 1 h soak [22].

elements as catalysts using the periodic table. tization as non-graphitizing carbons; (c) the use
Their failure in this may be due t o : (a) the use o f only 0.5 to 3 wt% of catalyst, amounts often
not only o f metals but also of oxides and car- t o o small to produce detectable changes.
bonates; (b) the use of a graphitizing carbon Weisweiler etal. [27], in a more systematic
which is n o t so susceptible to catalytic graphi- examination, heated a glassy non-graphitizing
312
T A B L E I Elements acting as a graphitization catalyst
Ia IIa IIIa IVa Va Via

Li Be B C N 0

[251 [65] [27] [68]


[26] [28] [69]
[52] [701
Na Mg A1 Si P S
[27] [281 [28] [831
[281 IIIb IVb Vb VIb VIIb 1 VIII i Ib IIb [651 [811
K Ca Sc Ti V CI Mn Fe Co Ni Cu Zn Ga Ge As Se
[281 [281 [28] [27] [281 [ 2 7 1 [27] [271 [281 [281
[33] [61] [28] [28] [28] [281 [501
[61] [85] [34] [60] [341
Rb Sr Y Zy Nb No Te Ru Rh Pd Ag Cd In Sm Sb Te
[34] [27] [251
[61] [281 [261
[90l [34]
Cs Ba La Hf Ta W Re Os Iy PA Au Hg T1 Pb Bi Po
[251 [33] [28] [34] [271 [251
[26] [33] [33] [26]
[34]
*The numbers in the Table are reference numbers

carbon crucible containing metals to temperatures VIIb metals have 2 to 5 electrons in the d-shell.
about 100 to 200 K above the melting point of They form strong chemical bonds with carbon to
the metal. Some metals reacted with the carbon form metal carbides. Hence elements of Groups
crucible to exhibit catalytic effects. However, IVb to VIIb and VIII are graphitization catalysts.
Weisweiler etal. noted that A1 and Si did not Known graphitization catalysts are listed in Table I
exhibit catalytic activity. This is because the in the form of the periodic table [33, 34, 35].
reaction temperature was too low and carbides Borides of rare-earth elements are reported to
and nitrides were formed during heating. be effective graphitization catalysts [36]. Boron
0 y a and 0tani [28] examined the catalytic is a very efficient catalyst and as such, mechanisti-
effects of 22 metals on both non-graphitizing cally, it should not be grouped in Table I.
(phenol-formaldehyde : 10 wt% catalyst) and graph- The co-ordination of catalytic graphitization
itizing (3.5 dimethyl-phenol-formaldehyde : 20wt% with diamond formation can also include the
catalyst) carbons, using optical microscopy and efficiency of catalytic cracking of hydrocarbon
X-ray diffraction techniques to detect changes. gases onto surfaces of transitional metals [37].
Reaction temperatures were 3100 K or 3300 K There is no available theory to explain the
at which graphitization had occurred or the metal catalytic graphitization by non-transition metal
had vaporized from the system. 0 y a and 0tani elements. 0 y a and 0tani [28] point out that
noted that the ability of transition metals to the majority of graphitization catalysts have an
graphitize catalytically corresponded with their atomic number of less than 40 and a first ioniza-
ability to synthesize diamond. See also [29, 30]. tion potential of between 6 and 8 eV.
The Group Ib elements were an exception. Group
IIb metals cannot react with carbon because of 3.2. A l l o y s as c a t a l y s t s
completed d-electron shells. Group VIII metals Alloys, as graphitization catalysts, behave differ-
have a d-shell occupied by 6 to 10 electrons. The ently from constituent elements. The lower
energy levels of such configurations change little melting point (eutectic) of alloys contributes
on acceptance of electrons from carbon (carbon to lower graphitization temperatures [38]. The
in metals is a positive ion [31, 32]). Group IVb to solubility of carbon in ferro-silicon alloys is

313
lower than in constituent elements [39]. For B203 is less efficient as a graphitization catalyst.
ferro-silicon alloys, the optimization of catalytic There are two possible reasons for this: one is
ability occurs with 25 wt% of Si in the alloy that when a high heating-rate is used B203 is
[40]. Although, in alloys of increasing Si-content, readily volatilized above 2150 K before conver-
the rate of nucleation of G-component graphite sion into B4C; the other is that B4C formed from
increases, the rate of diffusion of carbon in the B203 may be covered with an exterior layer of
catalyst decreases, so diminishing catalytic acti- glassy B203 [52].
vity. Oya and Otani [41] observed that with CeO2 exhibits catalytic activity but is not
ferro-silicon alloys containing more than 33 wt% effective with cokes containing sulphur. Ce2S3
Si, the ferro-silicon separates into FeSi and Si at is thermally stable and is easily formed from
treatment temperatures. The addition of a small CeO2 and S [38]. Addition of Ca to the system
quantity of Si (1 to 3 wt% Si) can suppress F%C removes the sulphur as CaS and permits the
formation in cast iron [42] as well as suppressing CeO2 to act as a graphitization catalyst.
the growth of large single crystals of graphite The complex clay minerals are effective graphi-
from an iron melt [43]. tization catalysts. In particular, celicite was
When aluminium and titanium are present studied by Ishikawa and Yoshizawa [53], who
together, the conversion of coke into the G- suggested, on the basis of the structural similarity
component graphite is more complete than when between celicite and graphite, a pseudo-epitaxial
aluminium alone is used, although the mechanism growth of graphite on the surface of celicite.
is not obvious [44]. A fibrous carbon was Oya etaL [54] consider that the clay minerals
obtained from the decomposition of acetylene gas exert an activity at higher temperatures of decom-
on nichrome wire (Ni-Cr alloys) [45] but this position of the clay (1470 to 1770 K) as well as
study was not extended to a comparison using Ni at higher temperatures (2470 K) when the decom-
and Cr wires. position products of the clay exert their individual
catalytic activities. The catalytic activity of the
3.3. C o m p o u n d s as catalysts clay is initially attributable to its high reactivity,
The catalytic activity of a compound is sometimes resulting from its decomposition.
different from the activity of the constituent
metal or other compounds containing the same 3.4. Particle size of catalyst
metal. Both CaCO3 and Ca(OH)2 produce G- In an initial study Baraniecki et al. [40] observed
component graphite at their recrystallization for ferro-silicon alloys that an optimum particle
temperatures under high pressure, but CaF2 does size was 50 to 70 pm. The area of contact between
not [46]. The former two calcium compounds catalyst and carbon depends upon the size distri-
are said by Noda [46] to form unstable complexes bution in both systems [55, 56]. On the other
with carbon, leading to formation of the G- hand, the catalytic activity of SiO2, of particle
component. In studies of the manufacture of sizes 0.07 to 0.12 mm and 1 to 2 mm, towards
nuclear-grade graphites by Parker et al. [47] the an anthracite was not influenced by particle size
catalytic graphitization of a needle-coke by Fe, [51].
FeO, F%O3, Fe304 and FeSiO3 was attempted. Whereas, conventionally, catalytic activity has
The F%O3 was the most effective catalyst, produced essentially G-component graphite, the
yielding a graphite of high density and large use of more finely-dispersed catalysts has created
crystallite size, suitable for use with neutron a new phenomena, that is, the formation of
radiation [48, 49]. Yokokawa et al. [50] found Ts-component graphite [57-59]. Suitable organo-
that additions of Cu, CuF 2 , CuSiF6, CuO and metallic compounds are mixed with resin homo-
CuC12 behaved similarly because they all formed geneously to form a solution with monomeric
Cu initially in the graphitization treatment. materials subsequently polymerized to resins, etc.,
However, because of the remarkable catalytic which can easily be carbonize d (e.g. phenolic and
activity of Si in carbons at temperatures above furfury!alcohol resin). Also, a suitable solution can
2500 K, the use of FeSiO3 and CuSiF6, distinct be added to a powder of the carbon [11, 60-62].
from other Fe- or Cu-compounds, has to be The formation of this T s-component graphite may
considered carefully. be influenced by the presence of the organo-
Boron is a catalyst because it forms B4C [51]. metallic compound, or may be formed from it,

314
Ca)

I,I IJ

LLI=IL I I l l l i l
21 2'2 24 25 26 27 28 29 30
(b) 2 O (CuK~) (o1

Figure 4 (a) Optical micrograph of a phenolic resin carbon to which are added nickel particles (150#m diameter) prior
to heating to 2900 K [16]. A shows G-component, B shows Ts-component and C shows A-component. (b)X-ray dif-
fraction (002) profiles of carbon taken at A, B and C [66].

but these suggestions are not thought to be accu- metal diffuses into the carbon matrix. With
rate. increasing distance from the central nickel particle
Yajima and 0mori [63,64] detected free the size of diffusing clusters of atoms diminishes
atoms of iron, Fe+ clusters, iron clusters, super- as nickel is left within precipited G-component
magnetic and ferromagnetic iron in carbon from graphite. Thus, a stage is reached in this pro-
acetylferrocene-furfurylalcohol resin (at HTT: cess when a change in mechanism occurs because
673 K). Oya etal. [16] carbonized phenolic resin of the reduced size of the nickel particles and
doped with Ni-acetylacetonate to various HTT and formation of the Ts-component results [59,
observed catalytic activity and they were able to 66].
correlate particle size of Ni with activity. The T s- The phenomenon of formation of the T s-
component was found in carbons containing component graphite suggests further experi-
nickel particles of size about 20 nm. When the mentation into the effects of even smaller sizes
nickel particle was 80 nm only the G-component of catalyst particles, for example, the use of a
graphite was formed. substitution element in the carbon. In early
The addition of larger particles of A1 (74 to studies, Noda and co-workers [68-70] heated
250/~m) [59,65], Be (~ 74#m) [65] and Ni petroleum coke and a thermal black under an oxi-
(150#m) [66] to a non-graphitizing carbon pro- dizing atmosphere (02 or CO2). This atmosphere
duced, on heating, both G- and Ts-components. was effective in the homogeneous graphitization.
Possibly small sizes of metal particles were created of both carbons, that is, the A-effect without
during the graphitization process. Using a micro- formation of either G- or Ts-components. In
focus X-ray diffractometer (3ya et aL [66] observed studies of catalytic graphitization by metal
the G-component graphite existing around a void vapours, 0ya and co-workers [23, 71, 72] heated
created by the vaporization of a larger nickel the metal and powdered graphitizing carbon (from
particle (Fig. 4). The G-component graphite was 3,5-dimethyl phenol formaldehyde resin)and non-
surrounded by a shell of the Ts-component graphitizing carbon (from phenol formaldehyde
graphite. The crystallite size of the G-component resin) in a close graphite reaction cell. The metals
graphite decreased from the inner to the outer Ca and Mg exhibited the A-effect. Further, using
regions. A similar phenomenon was observed using a charcoal at a temperature above 1900 K, calcium
ferro-silicon [40] as well as nickel which was vapour also catalyzed the formation of Tn"
electro-plated onto the surface of carbon fibres component carbon.
[67]. During the graphitization process nickel Boron will exchange with carbon in the lattice
315
(substitution) and is also located interstitially. The boron is used because a larger amount of boron
presence of substitutional boron results in homo- is dissolved into a less-ordered carbon [94].
geneous graphitization, that is, the A-effect On the other hand, the preferential graphiti-
[73-77]. Additions of amounts of boron to a zation of anisotropic graphitizable carbon is
carbon in excess of the solubility of boron in reported using titanium, Murty etaL [95], and
carbon results in the formation of B4C particles by chromium, Mochida et aL [96]. It is thought
which, on heat treatment, lead to the formation that with crystallites orientated approximately
of G-component graphite [73, 78, 79]. parallel to each other but being prevented from
The technique of co-chemical vapour depo- growing into larger crystallites by carbon atoms
sition (Co-CVD) can be used to prepare carbons at the periphery of the crystallite, the chromium
containing homogeneous and finely dispersed may react with, and remove, these peripheral
particles of other elements [80-82]. Such a carbon atoms. Consequently, crystal growth
carbon containing O.18wt% Si exhibited very can occur.
significant catalytic graphitization [81 ]. This
content corresponds to the maximum solubility 4.2. HTT of carbon
of silicon in carbon. The carbon produced is Carbons of increasing HTT become more ordered;
probably A-component. A similar effect is ob- this tendency is more pronounced with graphi-
served using sulphur instead of silicon [83]. tizable carbons. Accordingly, carbons of increasing
However, the use of substitutional phosphorous HTT should be less influenced by graphitization
suppresses the graphitization process [84]. catalysts. This concept was examined by Oya et al.
[97] using carbon from a phenolic resin and
4. Properties of the carbon used finely-divided nickel particles, of particle size
4.1. General considerations 20 nm [16]. Larger amounts of the Ts-component
Fitzer and Kegel [85] and Gillot etal. [86] were found in carbons of lower HTT. In another
postulate that the formation of the G-component, study, Torikai etal. [98] heated mixtures of Ca
isothermally, results from the negative free energy or CaO with petroleum cokes of increasing HTT.
of transformation of carbon to graphite. This is The cokes with HTT of 1300 to 1700 K behaved
weU-established and frequently demonstrated, for similarly but the modification to cokes with
example by Presland and co-workers [87-89] HTT > 2100 K diminished significantly. Oberlin
who observed that, during the heat treatment of and Rouchy [99] report that increased amounts
an isotropic carbon, on one side of a metal plate of G-component graphite are formed when an
(Ni or Co) the carbon dissolves into the metal iron catalyst is heated with a non-graphitizing
and reappears on the other surface of the plate carbon of increasing HTT.
as G-component carbon. The catalytic activity
of A1, Be [651, Zr, Ti [90], Ca [911, Cu [50] 5. Experimental conditions of
and Ni [11] are explained in these terms. The graphitization
less ordered is the carbon the larger will be the 5.1. Method of catalyst addition
value of-- AG for the transformation into graphite. Graphitization phenomena are sensitive to methods
Gillot and Lux [92] used chromium to graphitize of addition of the catalyst to the carbon. Ts-
a non-graphitizing furfurylalcohol coke (doo2 = component graphite is formed on reaction of a
343 pm, Le = 9 nm) but were unsuccessful with a homogeneous mixing of urethane foam or naph-
graphitizing carbon. Wewerka and Imprescia [61 ] thalene diol with FeFa; without mixing, the G-
co-heated a less crystalline filler carbon with a component is formed [60]. This effect is no
more crystalline binder carbon with organo- doubt due to differences in the reactivity of iron
metallic compounds (Ti-oxyacetylacetonate, V- particles of different sizes. Similarly, the catalytic
acetylacetonate, Zr-acetylacetonate, etc.). Only ability of Si is very sensitive to the mode of
the Filler carbon was graphitized. Oberlin and addition of the Si to the carbon [58]. Additions
Rouchy [93] describe a non-graphitizing carbon of Si(OC2Hs)4 to a phenolic resin carbon, regard-
as consisting of a turbostratic domain with less- less of the methods of addition, always yield
ordered boundary carbon. This concept that the finely divided particles which produce the Ts-
less-ordered carbon is preferably catalytically component. Silicon particles of larger-size (44
graphitized must be carefully examined when to 57/ma) [58] produce the G-component when

316
buried in a phenolic resin carbon and the Ts- Mochida et aL [96] observed that chromium oxide
component when added into the phenolic resin exhibits different catalytic effects using a non-
carbon particle. In the former specimen, the graphitizing carbon. At temperatures of 1550 to
matrix (parent) carbon diffuses into the larger- 1850 K a process of homogeneous graphitization
sized particles of silicon to form larger-sized occurs, leading to production of the A-component.
particles of SiC when they yield the G-component Between 2200 and 2300 K the non-graphitizing
on evaporation of the silicon at 2473 K [100]. In carbon was converted into the G-component,
the latter system, the larger-sized particles of caused by the presence of molten chromium.
silicon evaporate and reprecipitate on the surfaces Gillot etal. [92] earlier reported the formation
of carbon particles to produce finely divided SiC of two phases of carbon using chromium as a
particles which yield the T s-component. catalyst. At 1300K the carbon had doo2 =
343 pm and L e = 9 nm. This presumably must
5.2. Amounts of catalyst added be the A-component. The G-component was
With increased percentages of catalyst in a carbon formed at 1900 to 2100K and remained un-
there is an increase in the extent of graphitization changed on heating to 3100 K.
of the carbon. However, the formation of the Ts- Baird [104] found that when propane gas
component can be replaced by the G-component, is cracked over nickel foil at 590 to 6 5 0 K a
resulting from the coalescence and growth of columnar carbon is formed, doo2 = 340 pm. At
finely divided particles of catalyst. Some catalysts, 650 K to 1070K a laminar carbon is formed
dependent upon the percentages present, can form doo2 = 336 pm [104]. Bulk diffusion and surface
A-, T s- and G-components. When less than 1 wt% diffusion mechanisms have been proposed to
of boron is substitutionally added to carbon, account for the growth of the columnar and
resultant graphitization produces the A-component laminar products, respectively.
[74-76, 79]. When 1 to 5 wt% of boron is present
in a non-graphitizing carbon the formation of the 5.4. Effects o f a m b i e n t a t m o s p h e r e
Ts-component is observed on heating to 2500 K The presence of oxygen and carbon dioxide can
[79]. when 10wt% of boron is present in a induce some form of graphitization phenomena
phenolic resin carbon then the G-component is [68-70]. Although nitrogen is not a graphiti-
observed at 2673 K [79]. The formation of the zation catalyst its presence appears to enhance
G-component by the catalytic action of boron or the activity of calcium as observed by Oya et al.
boron oxide is also reported for other carbons [23] and Hirano [105] when nitrogen was
[74-76,101,102]. replaced by argon in graphitization studies. It is
Marinkovic et al. [81] found that heat treat- thought that intermediates such as CaCN2 and
ment of a pyrolytic carbon containing 0.15 to Ca3N4 are more readily formed than CaC2.
0.2 wt% of silicon produced the A-component. Boehm [106] confirmed this behaviour by report-
Kaae [103] measured the sizes of silicon carbide ing the formation of graphite, doo2 = 336 pro,
particles in a pyrolytic carbon and found for during the production of calcium cyanamide from
10 wt% Si that the particles were about 20nm calcium carbide and nitrogen at 1270 to 1420K.
diameter and for 16 to 34 wt% Si particles were
about 100nm diameter and distributed non- 6. Mechanisms of catalytic graphitization
uniformly. Kaae does not report graphitization 6.1. The G-effect
behaviour but T s- and G-components can be This effect occurs with all carbons, regardless of
expected, respectively [16, 58]. the extent of graphitization, when large particles
of catalyst are used of size greater than about
5.3. Effects of graphitization temperature 100 nm. Two mechanisms are currently proposed;
Some graphitization catalysts behave differently one is the solution of carbon into the catalyst
at higher graphitization temperatures. Two reasons particle followed by precipitation as a graphite
may be considered. As discussed above, catalyst material (G-component), as outlined in Fig. 5.
particles can sinter and agglomerate with increasing This reaction can proceed isothermally because
temperature, leading to a cessation in production of the negative free energy change in going from
of the Ts-component , being replaced by the disordered carbon to graphite, see Fig. 6, [85, 86].
G-component [16]. Other catalysts may melt. It would appear that the metal catalyst need not

317
of silicon within a carbon from a phenolic resin
DISORDERED [58]. It is known that the ionic carbides of
CARBON M aluminium and beryllium leave behind the G-
component on evaporation of the metal at their
decomposition temperatures [107-109]. How-
ever, when alurninium particles are used as graphi-
tization catalysts, G-component material is formed
via the solution-precipitation mechanism.

6.2. The Ts-effect


T s-component material is formed on beating non-
graphitizing carbon with finely-divided catalyst
MCI-x -t-EC --"'~MCI-x.i-E MCI_x+E---,- MCI_X-I-E;G by a process not yet clearly understood. Oberlin
OR OR and Rouchy [14, 93] studied the catalytic action
M-t-(I-X)C---,'MCI_X MCI_x--~'M+(I-X)G of iron powder, in small concentrations, upon
powdered saccharose carbons with HTT of 1873
l~gure 5 Diagram showing how, during the migration of
a metal carbide particle through a carbon matrix, the and 2073 K. Using TEM, SEM, electron diffraction
particle dissolves relatively disordered carbon and pre- and optical microscopy they observed that iron
cipitates graphite [86]. appears to react preferentially at the boundaries
of the turbostratic elementary domains which
be molten at the temperatures involved, nor need a constitute these non-graphitizing saccharose
stoichiometric compound with carbon be formed. carbons. In this process, droplets of iron carbide
The temperature for catalytic graphitization by a are formed, on the surfaces of which float
metal is not changed by its particle size. Yokokawa detached elementary domains. On decomposition
et al. [50], in a study of catalytic graphitization of the carbide, a shell of carbon is formed which
by copper, observed unidentifiable X-ray diffrac- is graphitizable because the carbon lameUae are
tion peaks, thought to be from a copper-carbon parallel to the external surface of the spherical
compound. hollow shell. In this model it is assumed that iron
The second mechanism involves the formation reacts preferentially with carbon atoms in the
and decomposition of carbide intermediates. This boundaries of domains thus enabling the domains
mechanism is dearly observed using large particles to float on the surface of the droplet.

.,el
FREE ENTHALPY OF GRAPHITE
p : lOOatm
\
!\~ DISORDEREDSTATE
I]\ /
-.-- I ! '~( MELTING POINT
"r.~... ,X , ,- , , , -
3"r
~ x
3000 4000 ~ooo 6000 7000 T(K)
9'\i \
, -10
"x. \
\3
E
g ~ ~ x HEATOF FUSION: lOKc•llmol
ENTROPY O F F U S I O N : 2,5ca[/grad.mo[

ORDERED STATE

450 Figure 6 The variation of free


energy of graphite with tem-
perature. The free energy of
"disordered" carbon is also
shown [85].

318
Another mechanism is the solution of carbon between the small elementary domains of struc-
into the freely-divided catalyst particle followed ture in the saccharose carbon will become
by precipitation, as suggested for the formation less rigid on heat treatment so facilitating re-
mechanism of the G-component [66]. As with a arrangement into small but better orientated
nickel catalyst [16] when nickel particles, 20 nm domains.
in size, are used it is not possible to form the G- Henning [111] and Kotlensky etal. [112]
component, of size 80 nm; instead Ts-component suggest the mechanism of diffusion of boron
of size 11 nm is formed. through the carbon lattice, not supported by
Tomita etal. [110] decomposed benzene Rouchy and Mering [73]. Marinkovic etaL
vapour on nickel at a temperature of 1073 K. The [81], in studies of siliconated pyrolytic carbon
resultant carbon, d0o~ = 339 pm and Le = 12 to (Si-PC) also used the mechanism of migration
16nm, contained finely-divided nickel particles of Si through the carbon lattice to explain graphi-
(of size 20 to 30 nm) thought to act as active sites tization.
for carbon formation. The X-ray parameters of
this carbon and the particle size of nickel are very 6.4. The T n-effect
near to those observed by Oya etal. [16] in a Heat treatment of a non-graphitizing carbon,
Ts-component (dot2 = 342 pm and L e = 11 nm) without catalyst, occurs because of localized
formed from phenolic resin carbon by the internal stresses set up by anisotropic thermal
catalytic action of finely-divided nickel particles expansion within the carbon crystallite [18,113,
(of size 20 nm). The mechanism of formation of 114]. This stress is released by breakage of cross-
carbon from benzene on a nickel surface suggests linkages, resulting in the Tn-component and then
the mechanism of formation of the Ts-component. the G-component (multi-phase graphitization).
It is speculated that if gaseous calcium species
6.3. The A-effect are present in this system, they can react favour-
A-component material is formed on heating ably with cross-linked carbons to remove them.
carbons in the presence of 02 and CO2 [68-70], The Tn-component is formed in larger amounts
the vapour of Ca and Mg [23, 71,72] and ele- at lower temperatures when gaseous calcium
ments substitutionally bonded into the carbon species are present. This mechanism is essentially
lattice [73-77, 81,83]. Noda and co-workers the same as that for the A-effect by an oxidizing
[68-70] explained the formation of such carbon gas or calcium and magnesium vapours. In this
by an oxidizing gas. Defects within the crystallites review, however, the Tn-effect is distinguished
develop during the graphitization process. Such from the A-effect because such large amounts of
defects prevent the growth of lattices. It is prob- the Tn-component form only in the charcoal
able that such defects can react preferentially heated with calcium vapour.
with an oxidizing gas and are removed. Thus, the
hinderance to further crystal growth is removed 7. Changes in properties of carbon by
and extended graphitization results. The prefer- graphitization
ential reactivity may also extend to reaction It is possible to graphitize carbon fibres by heating
with Ca and Mg vapour [23, 71, 72]. nickel-plated fibres [67, 115]. The crystallinity of
Two mechanisms are proposed to explain the the fibre was improved but the fibre was too
A-effect of boron substitutionally bonded into brittle for commerical application.
the carbon lattice. Rouchy and Mering [73], in A similar degradation in mechanical properties
studies of catalytic graphitization of a non- of glassy carbon, heated with iron particles is
graphitizable carbon from saccharose, suggest a reported by Kammereck etal. [62]. A bi-phase
new mechanism involving a modification to the system is probably produced, so creating consider-
electronic properties of such cokes when the able internal stresses within the material resulting
amounts of boron added are less than 1 wt%. No in a higher electrical resistivity, despite an en-
B4C is detected. The diffusion of boron through hanced crystallinity. Parker etal. [47] prepared
the lattice of the carbon is rejected. Boron sub- artificial graphites, from a filler coke and binder
stitution is thought to create electronic defects pitch containing several catalysts. Every catalyst
and hence to modify significantly the electronic produced a material with increased electrical
properties of the carbon. The cross-linkages resistivity and decreased thermal coefficients of

319
' GrQphite

1111 II1[[
Limitof ~rain
Figure 7 Model for converstion of non-graphitizing carbon into graphitizable carbon, that is the Ts-component [93].

expansion. Flexural strength increased following the graphitized material [62]. However, the
addition of Fe203 but decreased following addi- formation of the A-component by using a sub-
tion of A14C3. stitutional element for catalytic graphitization
According to Trask [52] the addition of at tends to be free from the above deterioration
least 3 wt% of boron into synthetic graphite from in quality [52]. This is because the mechanism
petroleum coke and coal-tar pitch binder enhanced is one of improvement of an already existing
the crystallinity of graphite, improved its oxi- structure rather than the creation of a new material,
dation resistance and decreased the coefficient of for example by solution and precipitation for the
thermal expansion without causing any deterio- G-component.
ration in the flexural strength. Addition of I wt% Further to catalytic graphitization, additions of
of boron to pyrolytic graphite formed at 1803 K boron are used to sinter carbon particles under
also considerably improved the oxidation resist- hot-pressing 20MPa. Kobayashi and co-workers
ance. This doped pyrolytic graphite had a high [102, 118] fabricated carbon artefacts of density
density, p = 2.19 g cm-3 , a value of Le of 15.8 nm 2.02 g cm-3 and compressive strength 60MPa
and a highly preferred orientation of crystallites from 10wt% of powdered boron oxide in a
[75]. Kotlensky and Martens [116] state that the calcined coke powder. Molybdenum carbide M%C
pyrolytic carbon doped with boron exhibits a and zinc carbide ZnC may also be used for the
larger fracture elongation than the non-doped same purpose [119, 120].
pyrolytic carbon. Marinkovic etal. [117] substi-
tuted small amounts ( < 4 wt%) of phosphorus Acknowledgements
into a pyrolytic carbon. The resultant carbon AO acknowledges leave of absence from Gunma
increased its apparent density, microhardness and University, Japan, to study in the University of
lattice strain in the c-direction with no change in Newcastle upon Tyne. HM is gratefully appreci-
its oxidation resistance. ative of the support from the grant ECSC/7220-
Although Fig. 4 indicates that the G-component EB-815 from the European Coal and Steel Com-
is a well-orientated graphite the isolation of the munity supporting research in the Northern
crystallites does not permit strong bonding to Carbon Research Laboratories.
give a coherent material. Hence, catalytically-
graphitized material tends to have unsatisfactory References
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322