VOL 35, NO.

11
JOURNAL NOVEMBER 1, 1952

of the

American Ceramic Society

Properties of Graphite
by JOHN P. HOWE
Research laboratory, General Electric Company, Schenectady, New Yark

The structure, thermal properties, electrical

characteristics, and mechanical behavior of
graphite are reviewed and the highly anisotropic
character of graphite crystals is emphasized.
The interesting properties of graphite are due in
large measure to the strong semimetallic bonds
between carbon atoms in plane layers and to
the relatively weak binding between planes.
Details of its structure are due in part to the (A)
Frank dislocation mechanism for growth of crys-
tals. Thus graphite has a low vapor pressure I
and approximately two-dimensional electrical
and thermal conductivity. It is easily deformed C
in slip on the basal plane, but in polycrystalline
form it is relatively strong at high temperature.
Its lamellar nature is emphasized by its reaction /C\
1
with alkali metals and bromine.

( B) (D)
1. Introduction
DIAMOND CRYSTALS GRAPHITE CRVSTALS
IS'I'KAV,U.~~ST carbon atorris can be bonded together to Fig. 1. Two types of carbon valence bands. (A) Drawings of two farms

T form a solid in two ways, as shown in Fig. 1 . Diamond,

in which classical carbon-carbon single bonds join each
atorn to four others, each at the corner of a regular tetrahedron,
of diamond crystals. (6) Tetrahedral arrangement of carbon atoms in
diamond. (C) Drawing of a graphite crystal. . (0) Trigonal arrangement
of carbon atoms in graphite.
is the hardest substance known. It is, however, slightly
less stablc than graphite, one of the softest substances known,
in which each carbon atom is bonded to three others to make
111) a large phnc molecule. 'l'hrse planes in turn are stacked
togcther relatively loosely to make a crystal, in it manner to this discussion, the structure of tlic ideal graphitc crystal
l)e described latcr. and its deviations arc useful. The thermodynamics or
'I'hat tetravalent c;lrbon atoms could be bound as firnily enqetics of the more important dxanges graphite can undergo
will1 three bonds as with four was first suggested by Kekul6, are also required. Finally, the properties that are important
although hc used the idea of double bonds. Quantum mc- in the uses of graphite can be discussed. KO attempt is
chanical dcscriptions have been offered showing the main made to review completely the information on graphite,
fraturcs of such Ix)nds, which are so important in the chemis-. as it is very extensive. Rather, evidence for the illustra-
try of aromatic carbon conipounds. The large amount of tive or characteristic properties is presented.
work on the dcscription t d carbon and carbon compounds
Croiii lirst 1)rincinlesmakes it interesting to see to what extent
II. Crystal Structure
the iiiiportcint properties of graphite can he understood. Ihr (1)
The /deal cry&
What might tie termed the ideal graphite crystal structure
:It Lllc Irifty..Fourtll ~~~~~~~~l
t~rrsclltctl ~i ~ , ~ , wax proposed by Rernal' in 1924 arid is shown in 17i'iR.2. 'l'hc
, ~ ~ ~' ~ 1~ ,~~~~~~~i~~~
Ccraiilir Society, Pittsburgh, Pa., April 30, 1952 (Refractories
Ihisioii, So. 20). Kcceivcd April 19, 1963; reviscd copy rc-
rrivrtl July 7, 1962.
The author is rrsrareh associate, (kiicral Physics Kescarch 1 j. 1). Rernal, "Structure of Graphite," I'YOC.Roy. Sot.
I )q):irtiiiciit, Rrsrarrh I,:ihorntory, General 'f<lrctricCompany. (Lonrlon), A106 17401 749-73 (1924).
275
 Journal of The American Ceramic Society -IIozze Vol. 35, KO. 11

Fig. 2. Hexagonal structure of graphite. ( A ) Cn = 6.71 a.u.; (8) Ao = 2 4 6 a.u.

Fig. 3. Rhombohedra1 structure of graphite.

Fig. 4. An orthorhombic structure.

icgular lic~agoiial riiig armiigeiiieiit of the atoms in each
1)lam agrees with our knowledge ahLhout aromatic hydro-
lwhons, :md is the logical end result of building larger and
larger tnolecules in the series, for exainple I)enzene, naphtha
lcne, anthracene, and coronciic. Why the planes stack as
t tic?; appear to is not clear. I n fact. one might like to believe
lhaL thc structurc in Fig. 3 is to be preferred. I k b y e anti
Schemer: proposcd this structure and concludrd that amor
phous carbons are finely divided graphite.
Slokes” coricluded that certain weak X-ray refl
iouiid by Pinch and \\’jilmand(~’in electron diffraction and
showri riot t o come from the Iiexagonal structurc, could he
explained 1))- a proper admixture of the rhombohedra1 struc-
ture mith the hexagonal. Avorerecently, Lukesh5 has shown
that the strongest of the reflections used by Lipson and Stokes
‘ire ititrodttcd whcti tinliir:il graphite is treated with hromine,
thus suggesting ;ti1 inipuiity origin of the rhoinbohedml
\tructure I,ukc\h” also has shown that X-ray diffraction
I’ 1)ebyc mid 1’ Schcrrcr, “Interfcrenzcn an rcgellos oricsii-
tiereri Teilchen im Kbtitgeiilicht, IIT,” I’hysik Z , 18 [13] 291-301
(1917)
€3. Lipsoii and A. K. Stokes, “Struetiire of ( h p h i t e , ” /’tor.
KOY SOG.( L o ~ d o t ~A181
) , [984] 101-105 (1942).
4 ( a ) G. I. Finch and 13. Wilman, “I)iffr:tction of I<lectrons by
Graphite,” Prnc. Roy Soc (Lnndoiaf,A155 [SSti] 3 4 5 f i 5 (1936).
( b ) I?. A. Taylor and I). Laidler, “Anornalous Iliffractions in
IIull-I>ebyc-Sr€icrrcrSprctriim of <>raphite,” i\Jatzup, 146 [3A9 I J
130 (1940)
5 J.. S. ’ Lukcsh, “Anomalous S-Ray Diffraction Spectra iu
Graphite,” J . Chem. Phys., 19 [9] 1203-1204 (1951).
1. S . Luke\h, “Svnimrtry of Graphite,” PBys. R e v . , 80 121

Fig. 5 . A screw dislocation on surface of a simple cubic crystal.
1);ttlcmis of iiatiiral graplfitc singlt crystals show reflections
tli;tt are iiot given by either structure and that require, among
othtr things, twinning caused by discrete rotations of parts
ol the crystal about the c axis. Thus the details of the strue-
lure of graphite are not yet clcar, although 1,ukesh has worked
out one way 01 resolving the dificulties. I k will publish
his results soon.
It is interesting to note that slill another possible structure
has I)ecri proposed by h k e s h and I ’ a ~ l i n g as
, ~ shown in Fig.
.I. 13y a slight distortion the hexagonal rings, observed
rctlrctions can be accounted for aild, furthermore, the twin
rclationships an be understood. Ik-tlier work hy Lukesh,
Iiowcver. makes thcir interpretation dubious.
(2) Mechanism for Growth
More recently, theories and nieclianisni of crystal growth
having a bearing on the details of the structure of graphite
liavc been proposed and demonstrated.R If graphite crystals
grow, as proposed by Frank, by adding atoms to the edges
of a sicrew dislocation in the manner shown in Fig. 5, then
the \tacking of the planes and the details of the structure are
tietri mined by tlie growth process. Hortl“ has found spirals
on natural and artificial graphite crystals, as shown in Pig. 6.
‘These spirals 1)econir visible under the microscope when a
number of growth centers have combined to give a step of a
few liundred angstrom units. Areas that show no spirals
may Iiave many screw dislocations that happen to combine to
givc smooth areas or steps too sinall to be seen. Not all
graphite crystals show growth spir:tls, but those that do not
liave been deformed.
Most crystals of natural graphite are soniewliat inipure,
arc often deformed, and show twin markings. Their density
is close to theoretical (about 2.25 gin. per Artificial
graphites are porous and have bulk densities of 1.(i to 1.8
gin. per ems. ’They may be m : ~ khighly pure. IIiglier
densities also can hc achieved.
(3) Carbon Blacks
’l‘lie forination or carboil blacks from Iiydrocnrl~oiibdoes
not appear to follow the foregoing picture of growth in the
first stages. 13iscoe arid Gild that in the carbon-
I)laclr particles, carbon atonis are arranged regularly in hcxag-
’‘ .I.S. 1,ukcsh a t i d I,. I’auliiig, “Probleiii of Graphite Struc-
(wJL., 35 11 /21 125-28 (1!150).
” ( a ) 1‘. C. Vruik, “Influence of 1)islocatiotis oil Cryst:iI
(>rowtli,” I)iscussions Faraduy SOC.,1949, S o . 5, pp. 48-54.
( 6 ) I?. C. I h n k , “ ( h w t h of Carborundum: 1)islor:Ltions a i i t l
I’olyiypisni,” Phil. M o g . , 171 42, 1014--21 (1951).
!I V. 11. IIorii, “Spiral Growth on Graphite,” Nafzrre, ill press.
lo 1. Hisroe ail(/ 13. 1C. R:arrcn, “.%Ray Study of Carhon
Hlac*k,” J . .4pP/icd I’hys., 13 161 364-71 (1942).
277
Fig. 6. Photomicrographs of spirals on graphite crystals. ( A ) 1 lox; (B)
220x.
otial rings in thc planes (o directioiis) atid llial the j;lanes
are stacked approximately equidistant and parallel There
is complete disorder, however, in the orientation of the planes
about their norm:tls (the c direction), and the spctcing of the
p1:ines is slightly greater than in graphite. As the carbon
black in this turbostatic condition is heated above 1000°C.,
hydrogen is evolved, the dimensions of the regions in which
parallel-layer groups exist increase, and the graphitic order-
ing of the planes takes place, so that, at 3800°C., true graphite
crystals approxi1n:ttely 40 by 70 a.u, in tlie L mid u directions,
1 espectively, are produced.
Little grain growth appears to occur in graphite, a t least
under commonly attained temperatures of Lpphitization.
It is reported, howex-er, that each small particle” can be
converted into a crystal. That this process is influenced by
impurities is apprently the b of Acheson’s patent for
making artificial graphite.
The formation of carbon blacks would appear to involve
condensation of hydrocarbon molecules to form large aro-
inatic molecules, which stack like cards, parallel, but a t ran-
tlom otherit-ise. As the temperature is raised, the hydrogen
a t the edge of the large plane molecules dissociates and carbon
tttoms move, pro1xtbly building up graphite crystallites by
the mechanism of l‘rank.8 The planes least stable hecause
of shape or size are consumed first. Hydrogen atoms bonded
to the edge of these large plane molecules can make elongated
molecules more stable than square ones because, as Bradburn,
Coulson, and l i u s h b r ~ o k e ~ ~show,
( a ) the energy of the carbon-
hydrogen bond gives a negative edge tension. Impurities
can both initiate screw dislocations and provide surface
media through which carbon atoms can move more e a d y .
A still less-well-defined cl.ass of carbons results from char-
ring sugar and other organic compounds a t temperatures no
higher than 1000 “C. Riley“ concludes that the hexagorial
structure is not developed completely, but that some rings
are rotated out of the planes. X-ray diflraction shows that
the c spacing of the planes is even greater than in the carbon
blacks and that the planes themselves are poorly defined.
I n summary, the forms of carbon related to graphite that
have been descrilied are as follows:
(1) Xatural gaphites made up of easily distinguished
crystals, which may be twinned and distorted in other ways
but which consist essentially of planes of hexagonal rings
stacked a b a.
(2) Artificial graphites containing crystals extending 50
to 100 a.u. in thc u direction aiid 20 to 60 a.u. in the c direc-
tion, but otherwise similar to the above ; and artificial graph-
11 I f . I,. Riley, “Amorphous Carbon a ~ i dGraphite,” Quart.
Revs. (London), 1 111 59-72 (1947).
 2’78 Journal of Il ‘he Arnev.ircin Cerarnic Society- --IIowe Vol. 35, No. 11
1 1 1 1 1 1 1 1 1 1 1 1
C (SOLID,GRAPHITE) = C (SOLID, DIAMOND)
1600- GRAPHITE
-
I400-
n=2.00f0.01
I200F ’ A
-
&!
1000
/ - I

80Ob /

: - 200O
-400t1 I I I I I I
200 400 600 .. 800
TEMPERATURE rd
Fig. 7. Difference in free energy between graphite and diamond as a
function of temperature and pressure. Values below zero indicate within
limits of uncertainty the region in which diamond is thermodynamically
more stable than graphite.
Table 1. Heats of Dissociation Related to Heat of Sub-
limation of Graphite
CO( g ) = C(g) + O(g) AIf *210.82, 227.04, or
=
256.1 8 kg.-cal./mole
C(h) -1- ‘/J)2(g) = CO(g) AT[ = 27.202
O(6) = ‘/eOzk) 111 = 58,586
* lIerzbcrg, footnote reference 18,
ites with crystals extending more than 1000 a.u. in the (z
direction.
( 3 ) Carbons inticli like very linely divided graphite but
containing planes stacked nith random rotations about the c
xis (turho5tatic). IIydrogeri and other impurities on thc
edges of t h e planes arc important in determining the proper-
ties of these carbons.
(4) Carbons in whicli some disorder is present in the planes
‘ind possibly some bonding between the planes. Aromatic
cark)on-carbon bonds arc dominant, but some single tionds
may exist. Impurities such as hydrogen, oxygen, nitrogen,
and boron are probal)ly important, and their presence depends
on the source or the carbon.
111. Electronic Structure of Graphite
’I’he sCal)ility of graphite at high temperatures in the
itbscncc of oxidizing agents arid carbide-forming metals is
due to the very strong carbon-carbon bonds in the planes
\Vc arc uow used to the type of bond in aromatic hydro-
carbons in which part of the binding energy is prorided by
electrons not confined t o any given part of the structure.
The extra hinding energy is usual1y called resonance energy,
l)ecause it can be described as resulting from the superposition
of two or niorc electronic structures or spatial distributions
of electrons to approxinmtc a n actual distribution. The
rrsorraiit iriteraction of tlie superposed distributions gives rise
to a binding energy that may he estiinated by methods of
quantum iiiechanical perturbation theory. Thus in gaphitc,
on tlie average, three electrons form standard single carbon-
carbon bonds and one electron per atom provides additional
binding to each of the thrcc nearest neighbors.
When in solids the energy lcvels (bands) and their p o p l a
tion are such that sonic of the electrons may inow through-
I , I id
I000 1200
Fig. 8. Dependence of specific heat of
grophite on temperature a t low tempera-
tures.
out the crystal, electrical conductivity results and the sub-
stance is usually thought of as a metal. The problem of the
electronic structure of graphite has been treated by
by Coulson, I3radhurn, and R~shbrooke;’~ ( a ) ~ ( b ) ~ ( cand
) by
Ihrriol and ,\/Ietzger.13(“) \&’a&ace uses molecular electronic
orbitals sclectcd for the mobile electrons and computes their
behavior, i.e., the electrical and magnetic properties. Coul-
son, Bradburn, and Rushbrooke consider the planes large
molecules, construct molecular orbitals by taking linear
combinations of atomic orbitals, and calculate stabilities
of various-shaped crystallites as well as the distribution of
electronic states versus energy. I3arriol and Metzger use
molecular orbitals that satisfy the periodic boundary condi-
tions for graphite crystals and compute binding energies.
Their calculation for the heat of sublimation of graphite to
carbon atoms is 124.5 kg.-cal. per mole.
The binding between layers has been studied theoretically
by B r e n i i : ~ n . ~He
~ computes only the repulsive forces from
the inolecular orbital electronic wave functions for the crystal,
and assumes a van der W a d s type of attraction of magnitude
to give a correct interplanar distance. He calculates that
interplanar forces contribute only 3.99 kg.-cd. per mole to
the stability of the graphite crystal. The difference in energy
calculated for the o1)served stacking versus one in which the
atoms are all in register is so small as to suggcst that at high
temperatures no order should exist in the stacking, contrary
to observation.
l 2 P. I<. Wnllacr, “Band Theory of Graphite,” Phys. Rev., 71
[!I] 622-34 (1947).
l 3 ( a ) Mary I<mdburn, C. A. Coulson, and C. S. Rushbrook:,
“Graphite Crystals and Crystallites: I, Binding Energies in
Small Crystal Layers,” Proc. Roy. Soc. I<didinburgh, 62A, 336-49
(194%’).
‘ ( b ) ’c.A. Coulson m d (>.S. 1tushl.n-ooke,“Graphite Crystal\
and Crystallite?: 11, Energies of Mobile Electrons in Crystallite5
Infiiiite in One Direction,” zbzd., pp. 350-59.
(c) C. A. Coulson, “ISnergy Bands in Graphite,” f i a t u r f , 159
140341 265-66 (1947).
( d ) Jean Ilarriol and Jacques Metzger, “Application of Molecu-
lar Orbital 1Iethod to Graphite Network,” J . chim. phys., 47,
4 3 2 3 6 (1950)
l4 R. 0. Hrentiari, “Interlayer Binding in Graphite,” J. Chem.
Phys., 20 [ l ] 40-48 (1952).
Novcmber 1952 Properties of Graphite 279
M ullikenlb suggests that forces between planes may be
partidly due to electron transfer arid that this type of binding 2.21
would account for the observed stacking.
20 -

18-
IV. Properties of Graphite
- 16-
?’he characteristics of graphite that are used to advantage 0
14--
:ire ( 1) stability a t high temperatures, (a) electrical conduc- \

tivity, and (:<) crystallirir anisotropy arid weak binding be- 12-
tween planes. 4
5
-. 10-

(I) Thermodynamic Properties -i O 8 --

““0 6
’I’he basic reasons for the stability of graphite have already
Iiccn given. Calculation alone, of course, does not yield 04-

accurate values €or bond energies or heats of reaction. Ac- 02-

curate measurements have been made of the heats of combus-
00.
t ion of graphite and dianiond.IG IJsirig these values together 0
with measured heat capacities and compressibilities, Wagman TEMPERATURE (OK)

:tnd his co-workers16 computed the free-energy diffrrence Fig. 9. Specific heat of graphite. Curve (A): DeSorbo and Tyler, foot-
note 23; (squores), W. Nernst,”Der Energieinhaltfesterstoffe,” Ann. Physik,
Iictween graphite and diamond as a function of temperature 36, 395-439 ( 1 91 1 ); (solid circles), A. Magnus, “Specific Heats of Carbon,
and pressure. as shown in Fig. 7. Iiates of transformation Silicon, and Silicon Carbide,” Ann. Physik, 70, 303-31 (1923); ( X I S ) ,
of diamond to graphite are appreciable a t temperatures of C. J. Jacobs and G. S. Parks, “Thermal Data on Organic Compoundr:
wveral hundred degrees. Pressures of more than 20,000 XIV, Some Heat-Capacity, Entropy, and Free-Energy Data for Cyclic Sub-
stances,” 1. Am. Chem. SOC., 56, 1513-17 (1934). Curve (8) (diamond):
atmospheres therefore would be rrqiiired to transform graphite K. S. Pitzer, “Heat Capacity of Diamond from 70° to 300°K.,” 1. Chem.
to diamond. Phys., 6,68-70 (1938).
12 basic thermodynamic quantity, the heat of sublimation
of graphite, is lcss well known, in spite of a great deal of
rarciul work aimed a t determining the value by measuring
vapor pressures or rates of evaporation. Experimental work Table II. Entropy of Graphite at 298.16’K. (cal./mole/
by Ikewer, Gilles, and Jenkins17 appears to confirm the high degree)
value of a set of threr allowed by the possible values of the
Tacobs and Parks*
lieat of dissociation of carbon monoxide, as shown in Table I.18
Marshall and Sortonlq also obtained the high value in
1933 by rncasuring rates of evaporatioii. Objection has been 0 “-90 OK. extrapolated 0.182
90 ‘-298.1 OK. graphical 1.182
raixd l o these values on the basis that the accommodation -
cocflicient for the condensation of carbon atoms on graphite .S029R.16 1.36 f.0 02
may be siiiall and inay v with trmperature. Although 1)eSorbo and Tvlert
Hrewer, Gilles, arid Jenki report a careful test of this
point by showing that their results do not vary with the size 0 “-13 “K. extrapolated 0.004
13 ‘-298.16 “K. graphical 1.367
of the orifice of their Knudsen effusion cell, many other workers .

in the field are still not satisfied. I’uture work will resolve
this question.
Illhatever the heat of sulAirnation, the vapor pressure of
carbon reaches o m atmosphere only at high temperatures
(near 3600° to 37OO0C. (GT,OOo to (i700°1~.)).20 It appears,
inoreover, that the pressure a t the triple point is approximately
100 atmospheres ;21 consequently, direct observation of a
melting point is diKieult.
Much o f the equilibrium chemistry of graphite may be
rclated to the extrrisivc thermodynamic dala that have been
conipiled.lti~ 22
R. S Mullikeii, “Molecular Compounds and Their Spectra,”
J . A m CIcen? Soc , 74 [:3l 811-24 (1952).
1) I). W~tgnicm, 1:. Kilpatrick, W. J. Taylor, K. S. Pitzer,
and 17 I ). Ro\\iiii, “Heat 5, I‘ree ISnergics, and Equilibrium Con-
stants of Some Reactions Involving 0 2 , &, 1 1 2 0 , C, CO, CO,, and
CIla,” J . lirsrarch Nut1 l h r Stn?cdardy, 34 121 143-61 (1945);
IU’ 1834; Cryan? /Ib,tvacts, 24 151 94 (1945).
Leo Ihewcr, 1’. W. Gillcs, :md 1’. A. Jenkins, “Vapor Pres-
w r r and IIcat of Sublimation of Graphite,” .I. Chem. Phys., 16
181 797-807 (1948)
G IIcriberg, “Ilrat of 1)issociation oi the Carbon Mon-
oxide Molcculr and Neat of Sublimation of C:Lrbon,” Chem. Revs.,
20 111 145-67 (1937).
I” A. L. Marshall and I?. J. Norton, “Vapor Pressure and Heat
of \‘aporimtion of Graphitc,” J . An?. Chem. Soc., 55 [ 11 431-32
(1 W 3 )
nprrimcntal Rcalization of Melting of Graphite
Kg./Sq. Cm ,” Hrennstuff-Chem.,
s up t o 11,500
N.k. Chmey, V. C. Ikmistcr, and S. W. Glass, “Properties
of Carbon a t Arc Temperature,” Trans. Rlectrochem. Soc., 67,
107 50 (1935); Ceronz. Absfracts, 18 [91 245 (1939).
s 029R.1ti 1 . 3 7 1 5 0 005
* For referencc, see caption of Fig. 9.
t Footnote referencc 23.
22 ( a ) F. R. Bichowsky and F. D. Rosini, Thermochemistry of
Chcmieal Substances. Reinhold Publishing Corp., Kcw York,
1936. 464 pp.; Ceram. Abstracts, 15 [lo] 317 (1936).
( b ) K. K. Kelley, “Data. on Theoretical Metallurgy: I, En-
tropies of Inorganic Substances,” U. S. Bur. Mines Bull., h-0.
350, 63 pp. (1932). “11,High-Tcrnperature Spccific-Heat Equa-
tions for Inorganic Substances,” ibid., No. 371, 78 pp. (1934);
Ceram. Abstracts, 14 [7] 170 (1935). “111, Free Energies of Vapori-
zation and Vapor Pressures of Inorganic Substances,” U. S. Bur.
Mines Hull., KO. 383, 132 pp. (1935); Ceram. Abstracts, 16 [ 6 ]
190 (1937). (With C. T. Anderson) “IV, Mctal Carbonates -
Correlations and Applications of Thermodynamic I’roperties,”
U. S. Bur. Mines Bull., No. 384,73 pp. (1935); Ceram. Abstracts,
16 [61 191 (1937). “V, Heats of Fusion of Inorganic Substances,”
U. S. Bur. Mines Hull., S o . 393, 166 pp. (1936); Ceram. A b -
sfracts, 16 [5] 162 (1937). “VII, Thermodynamic Properties of
Sulfur and Its Inoyanic Compounds,” U. S. Bur. Mines Bull.,
No. 406 (1937). VIII, Thermodynamic Properties of Metal
Carbides and Nitrides,” U. S. B u r . Mines Rull., No. 407, 66 pp.
( 1937). “IX, Entropics of Inorganic Substances; Revision
(1940) of Data and Methods of Calculation,” ibid., No. 434, 115
pp. (1941); Ceram. Abstracts, 20 [9] 226 (1941). “X, High-
Temperature Heat-Content, Heat-Capacity, and Entropy Data
for Inorganic Compounds,” U. S. Bur. M i n e s Bull., No. 476,
pp. (1949). “XI, Bntropies of Inorganic Substances; Re-
on (1948) of Data and Methods of Calculation,” ibid., No.
477, 147 pp. (1950).
Part VI was prcpared by the U. S. Bureau of Mines and is as
follows: ‘ T I , Revision of Entropies of Inorganic Substances,
1935,’’ U. S. Bur. Mines Hull., No. 394, 55 pp.; Ceram. Abstracts,
16 [ti] 191 (1937).
280 Journal of T h e American Ceramic Society
The lieat capacity of grapliitc is especially interesting be-
c:tuse the high degree of crystal anisotropy is manifested at
low tcrnperatures by tlic depmdeiice of the specific heat on
r
I .*-.2 One may think o€ the heat content as due to three types
of vibrations in the graphite crystal, as follows :
(1) Very low frequency waves involving motions of the
planes as molecules, soniewhat like an accordion.
( 5 ) Interiiiediate-frequericy waves with displacements
transverse to the plane, like vibrations o€ a drumhead or
waves in water.
( 3 ) High-frequency longitudinal waves moving in the
planes and iiivolviiig displacements that stretch the strong
carbon-carbon bonds
Kruriihanslz4has studied the spectrum o€ the normal vibra-
tional modes of a grapliite crystal and has shown that, over a
certain temperature range, the crystal behaves much like a
Lw-diinensional system, requiring that the specific heat
vary a\ the second power of the temperature instead of as the
third power, :is in three-dimensional solids. Qualitatively
it is because tlie low-frequency modes attain their classical
cquipartition value at very low temperatures that only two
degrees of freedom per atom are left to contribute to the
increase in specific heat with temperature. Figure 8 shows the
logarithni of expcrimentally determined values plotted versus
the logarithm of tlie Kelviii temperature. This work oi
1)eSorI)oand has iinproved the value of the entropy
of graphite at room teniperature. Their data are presented
.tnd suinniarbetl in 1%g.9 arid ’Table 11.
IIrat capacities for grapliitc a t liiglicr temperatures may
1)c obtained lrom tlie publication by the Kational Bureau
ol Standartis.
In addition to bcing more stable than dianiond by virtue
of hinding energy, graphite also possesses the greater entropy
at any tcnipcrature above 0 OK. because of the thermal vibra-
t ions possil)le atid the greater volume per atom.
(2) Electrical and Magnetic Properties
’I‘hc general rcatures of the electrical and magnetic proper-
ties may be undcrstood in terms of the work of Wallace12
and others.”j Thc~ideal infinite graphite single crystal on
tlic basis of these calculations lias the distribution of electronic
energy states versus energy shown in Fig. 10. Just enough
statcs lie below 150 l o house all tlie mobile electrons at OOK.
At higlwr tcniprraturcs, electrons are excited to states above
ICO, wlicrcupori 1)otli they and the vacant states below
contriliutc to the conductivity. According to U-allace, the
iiuiiil)er of free electroiis permitted by the Ikrmi distrilmtion
at rooiii tciiipcraturc is 2.25 x 10 per carbon atom Thus
the conductivity is low. The conducti\Tity depends not only
on the riutiibcr or carriers hit also on their scattering as they
tuove. Scatt eririg by lattice waves clccrcases very rapidly
;it low tcniprraturcs m d would permit the conductivity to
I)ccoiiic very large if 110 F)crm,iticnt scattering centers were
tal. Xeasured values o f the conductivity
r s iricrcase with decreasing ternperature,
but appear to reniaiii liriite in the range below 10°K It must
lie c-oncluded iron1 this behavior that scattering centers for
electron\ are present in real crystds and that the number of
carriers does not go to 7ero a t low temperatures. From Hall
cl‘fcct studics25i t can be further concluded that there is a
slighl cxce\s of electrons, but lheir donors are not known.
Graphites made hy bonding small particles with pitch followed
I)y grai’lii tizaiiori show increasing conductivity at room
W. 1)eSorbo :ind U‘.W. Tyler, “Specific Tleat of Graphite
21
Iron1 1:3’ t o :300”1< ,” f’hyp. /<w.,83 141 878-79 (1951).
J . liriirrili~iisl,‘“l’licory of Specific Heat of Graphite”; t o be
published.
2i J. J . 1)oiioghue and u’.1’. Ihtherly, “A Kew Method for
l’rcci4on Mr:i\ureriiciils of 1I;tll :nit1 M:~gticto Iie\i\livc Corf-
ficic.tits,” Rrzi fw\tymir/,fitY, 22 (71 513 I f i (1951).
Ilowe Vol. 35, KO. 1 I
Fig. 10. Distribution of electronic energy
states vs. energy.
temperature. At higher temperatures a maxiinuni is ob-
served, followed by a decrease.
Wallace estimates that the conductivity parallel to the
planes (a) is 110 times that in the perpendicular direction (6).
The measured values range from 1 0 2 to 105.*G This large
anisotropy is another manifestation of the two-dimensional
nature of graphite. Iliamagnetic susceptibility provides
another illustration of this nature also, both in theoryi2
and by exp~riment.~7
Incompletely graphitized carbons show different electrical
characteristics, their conductivities being less and, up to
very high temperatures, increasing with temperature. In-
completely proved suggestions in terms of molecule size and
edge impurities may be made to account for this behavior
Although the spirals provide an additional path for current
flow in the c direction, i t can be shown that the effect on the
anisotropy of the conductivity is ncgligible unless the density
of dislocations should exceed 1 0 ’ 0 per cm2.
(3) Thermal Conductivity
Two facts show that the thermal conductivity is not elec-
tronic as in metals: ( I ) the value of the Lorcnz, Wiedemann-
Fram ratio, which is the product of the electrical resistivity
and the thermal conductixity divided by the absolute tem-
perature and (2) the low temperature dependence of the ther-
mal conductivity. Rather, therrnal energy is transported by
crystal vibrations, and, although a theory is being developetl,
tlie exact reasons for the temperature dependence observed
by Tyler” and Bermant a t low temperatures are not known.
A major Pactor, however, must be the T 2 dependence of the
specific heat, and a simple theory would predict the same
dependence for the thermal conductivity if boundary and
permanent inperfections only scatter vibrational waves.
o m data obtained by Tyler, which vary somewhat
y than Z 2 . They are given here because they
appear to be better than values already in the literature.
A inore complete account will be publishetl later by Tyler.
Energy transport by thermal vibrations in crystals falls ofl
as T-l in the high-temperature region, owing to interaction of
various vibrational niodes. It is very likely that electronic
transport becomes the more important process of the two
types a t sufficiently high temperature. Finely divided
graphites or carbons owe their insulating value largely to
the [act that conduction through the gas surrounding each
particle limits the transport of helit.
26 ( a ) W. I’riinak and I
,. Pucks, “1~:lectrical Coriductivities of
Natural Graphite Crystal\,” /MI. Am. Pl~ys.Sor , 27 [a] 18
(1 952).
(2)) K. S. Krishnan arid S.Ganguli, “1,arg-e Atiisotropy of Elec-
trical Conductivity of Graphite,” NnturP, 144 136501 667 (1931).
2i K. S. Krishnan and S. Ganguli, “Temperature Variation of
Abnormal 1Jiiidirectional I>iamagnetism of Graphite Crystals,”
Nature, 139 135081 155-56 (1937).
A W. W. Tyler, private communication.
t I<. Derrnan, privatc cotnmunicatioti to W. W ’Tyler.
November 1952 Properties of Graphite 28 I
I 1 I I I I I I l l

0 AGoT CUT PERPENDICULAR TO TEMPERATURE (OC)

Fig. 12. Strength in tension of several forms of graphite as a function o f
0 NATURAL GRAPHITE BONDED AND temperature. Graphite grades (National Carbon Company terms):
( A ) AUF, ( B ) A W G , ( C ) SA-25, ( D ) C-18, ( E ) AGX.

@ GRAPHITIZED LAMPBLACK

Table 111. Types of Graphite on Which Strengths Have

I I I I I I l l I I I I l l Been Measured at High Temperatures
Approx. amount
TEMPERATURE (OK] Graphite Method of (h‘dphitization of oriented
grade* manufacture temp. (“C.) grains (%)
Fig. 1 1 . Thermal conductivity o f several types of graphite a t room
temperature and below; CS and A G O T a r e National Carbon Company AUF Extruded 3000 60
terms. AWG Molded 3000 30
SA-25 Molded 3000 1
c-18 Molded 2600 30
AGX Extruded 2600 40

(4) Mechanical Properties

The weak forces between planes permit graphite to slip
readily on the basal plane. This slip probably occurs without
the benefit of moving dislocations. The lubricating proper-
ties of graphite have been attributed to this phenomenon,
although Savage28has shown that another condition must
be met also; namely, the presence of adsorbed films of water
ammonia, or hydrocarbons. When such adsorbed materials
are absent, graphite bearings wear rapidly and the resulting
dust is a very strong adsorber of nearly any gaseous substance.
.Is most pieces of graphite put to practical use have a pre-
ferred orientation owing t o fabrication, the over-all strength
of the material is anisotropic and is greatest in the direction
of working. Although not a strong material, graphite is a
useful high-temperature structural material in applications
not requiring the presence of oxygen, in particular in certain
metallurgical and ceramic equipment and apparatus Per-
* National Carbon Company terms.
haps the most interesting and valuable feature is the increase
in strength with temperature to above 2400°C. (4350°F.)
Figure 12, taken from Malstrom, Keen, and Green,
illustrates the properties of several commercial artificial
graphites listed in Table 111. Few readily available materials
are stronger than graphite above 1600°C. (2900°F.).
The anisotropy of thermal expansion and the resultant
internal stresses in polycrystalline material must be important
in explaining the variation of strength with temperature.
It must also be remembered that the pores in artificial
graphites provide stress concentrations. At temperatures
sufficiently high for grain-boundary flow, some relaxation
of stress can occur. For some local stress to exceed the point
required for fracture, therefore, the average stress has to be

29 ( a ) C. Malmstrom, K. Keen, and L. Green, Jr., “Some Me-

28 H Savage, “Graphite Lubrication,” J . Applied
( u ) R. chanical Properties of Graphite at Elevated Temperatures,” J .
I’hys., 19 111 1-10 (1948). Applied Plzys., 22 151 593-600 (1951).
(6) K. H. Savage, “Physically and Chemically Adsorbed (5) F. E. Faris, I,. Green, Jr., and C. A. Smith, “Thermal De-
Vilms in Lubrication of Graphite Sliding Contacts,” Ann. N. Y. pendence of ISlastic Moduli of Polycrystalline Ckaphite,” ibid.,
A G ( LSci.,
~ . 53, 862-69 (1951). 23 [I] 89-95 (1962).
282 Journal of The American Ceramic Society-Discussion
greater at high temperatures than i t need be at low tempera-
i ~ ~ a similar explanation for t h e varia-
tures. M r o z o ~ s kgives
tion of strength with temperature.
Deforniation due t o t h e motion of t h e screw dislocations
required for growth would be shear in t h e c direction. T h e
author is not aware of evidence that this deformation mech-
anism operates
(5) Lamellar Compounds
There is not space here to discuss fully t h e subject of lamel-
lar compounds of graphite. Two cases, however, illustrate
t h e nature of t h e substance very interestingly and are there
fore mentioned briefly.
Potassium metal reacts readily with graphite t o form at
least two compounds, ClsK and C8K.31 It has been shown
t h a t the plane arrays of carbon atoms remain intact, and that
3O S. Mrozowski, “Anisotropy of Thermal Expansion and
Internal Stresses in Graphite and Carbons,” Bull. Am. Phys.
.TOG., 27 [ 1 I 47 (1952); abstract of paper presented a t Annual
Meeting of the American Physical Society, Columbia Univer-
sity, New York, January 31-February 2, 1952. An abstract of
this papcr also appears in Phys. Reu., 86, 622 (1952).
8‘ H. L. Riley, “1,amellar Compounds of Carbon,” Fuel,
24 [ l ] 8-15; [2] 43-53 (1945); Ceram. Abstracts, 194’7, July, p.
14Xd.
of Ilowe Paper Vol. 35, No. 11
t h e potassium atoms t h a t are probably at least partially
ionized are placed i n regular positions between the planes.
T h u s one can think of a n ionic compound with large plane
molecule ions having a negative charge held together by
positively charged ions ; both electrostatic and exchange
forces provide bonding. Other alkali metals react with
graphite in somewhat similar although less clear-cut fashion.
Bromine also forms lamellar compounds, one of which
appears t o be CsBr, although the stoichiometric relation is
not definite. Riley3I states t h a t the bromine cannot be
present as ions. Bisulfate and nitrate ions, however, may be
introduced b y electrolytic or chemical oxidation of t h e graph-
ite in t h e presence of these ions.
T h u s i t is attractive, if not strictly accurate, to think
of graphitic planes as plane amphoteric macromolecules form-
ing compounds with both electron donors and acceptors.
I n summary, t h e unique electrical, mechanical, and chemi-
cal properties of graphite are those of large plane molecules
i n which t h e strong bonding power of the carbon a t o m is
nearly, b u t not quite, satisfied b y bonds lying i n the planes.
Acknowledgment
The writer is grateful to J. S. Lukesh, W. W. Tyler, and J.
Krumhansl for many discussions of the structure and properties of
graphite. He owes much to F. H. Horn, W. W. Tyler, and W.
DeSorbo for the use of recently obtained information and for the
use of graphs and photographs for figures. Many other sources
of information also have been used and are hereby gratefully
acknowledged.

Discussion of Howe Paper by S. Mrozowski”

I>r. Howc has presented among other interesting information

the very important results of the recent unpublished work by
I k . Tyler and associates on the thermal conductivity of car-
bons I n spite of the great practical importance, carbons have
not yet becu systematically studied. The best available data,
until now, were presented by Powell and Schofield.’ The two
heavy curves in Fig. 1 represent the temperature dependence
of the conductivity for polycrystalline graphite ( G ) and for baked
carbon ( H ) as roughly obtained from their work. In the past
we all believed that the extension of curve ( G ) t o low tempera-
tures followed a curve obtained some time ago by Buerschaper
(dotted curve) and that :i maximurn in the thermal conductivity
was reached somewhere below -200°C.2 Dr. Tyler’s results
disprove Buerschaper’s work; the thin curve joining curve ( G )
in Fig. 1 roughly represents his findings as reported by Dr.
I [owe.
The t.hertna1 conductivity of carbons heat-treated to inter-
mediate temperatures has not yet been investigated. It might
he of interest, however, t o those who are using such carbons in
their products t o know at least approximately what kind of general
trend is expected. A system of predicted intermediate curves
is added in Fig. 1 (dashed curves). The main properties of
t.hese curves are as follows. On thc low-temperature side of
maximurn the heat conductivity must be proportional to the
specific heat C , and t o the crystallitc size L. On the high-tem-
gerature side the conductivity decreases almost inversely pro-

* Professor of Physics, University of Buffalo, Buffalo, New

York. 1000 2000
R. W. Powell and F. H. Schofield, “Thermal and Electrical
Conductivities of Carbon and Graphite a t High Temperatures,” Temp (“C)
Proc. Phys. Soc. (London),5 1 , Part 1 [283] 153-72 (1939); Ceram. Fig. 1. Observed and predicted thermal conductivities (solid and dashed
~ o ~ ~ ~ ~18c rioi
t . 7271
. (1939). curves, respectively) for variously heat-treated carbons as function of
S. Mrozowski, “Thermal Conductivity of Carbons and temperature. Curves: (G)polycrystalline graphite, ( 6 ) baked carbon,
Graphite,” Phys. Rev., 86, 251-52 (1952). {HI heat-treatment.