Baker 1971

NUCLEAR ENGINEERINGAND DESIGN 14 (1970) 413-444.
NORTH-HOLLANDPUBLISHINGCOMPANY
G R A P H I T E AS A N E U T R O N M O D E R A T O R A N D R E F L E C T O R M A T E R I A L *
D.E.BAKER
Battelle Memorial Institute, Pacific Northwest Laboratory, Richland, Washington
1. Introduction aceous materials, rather than mined as the natural

material. The terms carbon, baked carbon, and amor-
Graphite was used for the first large-scale Hanford phous carbon are used to describe products made
plutonium production reactors because of its good from carbonaceous materials and heat-treated to tem-
neutron-moderating properties and its availability in peratures less than 1500 C. Synthetic graphite and
large quantities. Subsequently, it has been selected as electrographite refer to materials in which the baked
the moderator and reflector for second generation carbon is heat treated (graphitized) at temperatures
Hanford Production Reactors, the Peach Bottom High greater than 2200 C in Acheson electric furnaces.
Temperature Gas-Cooled Reactor (HTGR), the Ultra Nuclear graphites are high purity forms of electro-
High Temperature Reactor Experiment (UHTREX), graphites. Pyrolytic carbon is a vapor-deposited,
the Molten Salt Reactor Experiment (MSRE), and the highly anisotropic form of carbon in which struc-
nuclear propulsion reactors KIWI and NERVA. tures near theoretical density are attained. Glassy
Several graphite moderated power reactors are in carbon, so-called because of its appearance and
operation in the United Kingdom, for example, properties, is an extremely fine grain form of carbon
Calder Hall, Bradwell, Berkeley and Hunterston, which having a low permeability to gases.
are carbon dioxide cooled, and the Dragon reactor,
which is helium cooled.
Other materials have greater moderating ratios, 2. Production and fabrication
but the low cost, established fabrication technology,
and good high-temperature properties in nonoxidizing 2.1. R a w materials
atmospheres are important advantages of graphite. A Nuclear grades of graphite are electrographites
major limitation of graphite is its susceptibility to produced by modifications of conventional graphite
oxidation at high temperatures. Also, it should be re- manufacturing methods, with special care being
cognized that the physical properties of the material taken to exclude high-cross section impurities such
are extremely dependent upon the choice of raw as boron. Most electrographites are comprised of
materials and the fabrication process. Thus, engineer- two basic ingredients: a petroleum-coke filler and a
ing properties such as strength, dimensional stability, coal tar pitch binder [1 ]. The wide range in graphite
thermal conductivity, and density can be varied to properties is due to variations in starting materials
meet special design requirements. and to modifications in the production process.
Graphite is a specific crystalline form of carbon The most commonly used filler materials are
which exists in nature in limited quantities. Most petroleum coke, metallurgical coke, anthracite and
manufactured carbon and graphite products are pro- lampblack. Of these, the most easily graphitized
duced by the pyrolytic decomposition of carbon- material is petroleum coke. Petroleum coke is pre-
pared by cracking a heavy refinery oil at approxi-
* Chapter 37 of the projected USAEC Reactor Materials mately 450 C and subsequent distillation of volatiles.
Handbook, 3rd edition. These operations establish the ultimate graphitizing
414 D,E. Baker. Graphite as a neu tron moderator and reflector material
potential of the coke which, in turn, determines to a

large extent the properties of the graphite made from I RawPetroleumCokeI
the coke.
(~ Caiclnedat ~ C
The binder may be any hydrocarbonaceous material
which leaves a carbon residue upon distillation. It I CalcinedCokeI
should be thermoplastic material which is solid at
room temperature and fluid at higher temperatures.
These characteristics allow thorough mixing of the
filler with the binder when hot, and yet enable a
formed article to hold its shape at room temperature.
Coal tar pitch is one of the most commonly used
I Cooled
binders. Other binders include furfuryl alcohol, sugars,
phenol formaldehyde, and thermosetting resins.
2.2. Manufacturing process

2.2.1. Electrographites
Bakldto 800 C
The processing steps in the production of a conven-
tional nuclear graphite are summarized in fig. 1.
The first step, calcination, removes volatile hydro-
carbons and preshrinks the coke so that volume igna~l with Pitch
changes can be controlled on subsequent processing. ItlzEIto-3000 C
Such control is especially important in the manufac-
ture of large graphite blocks [2]. I NuclearGraphite I
The calcined coke is crushed and screened, and the
fines are milled to a flour with grain diameters from Fig. 1. Flow diagram showing the materials and processes
2 to ~ 300/~. The coarser coke filler particles for used in the manufacture of nuclear graphite [ 1].
moderator graphite usually range from 0.4 to 0.8 mm
in diameter, and these are mixed with flour in about The formed "green" carbon bars are then packed
a 1 to 3 ratio to form a blend. The individual grains tightly in granular coke or a coke-sand mixture to
of coke that make up the blend are rough and irregular maintain their shape, and heated to about 800C.
in shape. Cokes from different sources fracture in This step converts the pitch from a thermoplastic
different ways. The high degree of crystal alignment material (softening point ~ 100 C) to an infusible
of needle-type petroleum coke causes the material to solid, with the evolution of hydrocarbon gases. Un-
fracture into needle or flake-shaped particles, whereas less the heatup is very slow (3 to 6 weeks), the escap-
particles of less-ordered cokes such as gilsonite or ing gases will crack the bars. During heatup, poly-
fluidized cokes are more nearly cubical or spherical. merization and cross-linking proceed within the
The coke blend is next mixed with a pitch binder binder and at the binder-filler interface. Above
at about 165 C, at which temperature the pitch is 450 C, a large shrinkage occurs as the binder hardens.
quite fluid. When the forming is done by extrusion, After baking, the carbon bars may be graphitized
the binder usually comprises about 25 w/o of the directly; however, more frequently they are impreg-
mixture. During extrusion, the asymmetric filler coke nated with pitch to reduce the porosity and increase
particles align themselves with their long dimensions the bulk density of the resulting graphite. Pitch im-
parallel to the direction of extrusion. This alignment pregnation is performed in a large autoclave at tem-
gives rise to the anisotropy which is observed in the peratures of ~ 200 C and at pressures of ~ 100 psi.
final product, since the crystalline layer planes are The bars are next stacked in an electric graphitizing
generally parallel to the long dimension of the coke furnace, surrounded by silicon carbide, coke, and
particle. When molding is the forming method utilized, sand to provide thermal insulation, then fired at
the coke particles are aligned in a direction perpendi- 2600 to 3000 C. The heating cycle requires 3 to 4
cular to the molding force.
D.E. Baker, Graphite as a neutron moderator and reflector material 415
days; cooling continues for about 10 days before the free-standing bodies, methane or natural gas at pres-
graphite can be exposed to air. During graphitization, sures of 10-1 to 10-3 atm is passed through a furnace
most of the gases are evolved below 1500 C. Between and decomposed, depositing carbon on a graphite
1500 and 2500 C, the main process is crystal growth, substrate at 1400 to 2400 C. Pyrolytic carbon coat-
with the internal structure still imperfect. Above ings on fuel particles are applied in a fluidized bed at
2500 C, continued minor crystal growth occurs, but temperatures in the range 1200-1800 C. Argon and
the major effect is increased crystal perfection due to helium may be used as hydrocarbon diluents to fur-
diffusion and annealing of crystallite imperfections. nish sufficient gas flow for fluidization. The fuel
The purity of graphite may be improved by either particles may be carbides, oxides, or nitrides of ura-
thermal or chemical purification. Thermal purification nium, thorium, and/or plutonium. The carbon coat-
consists of heating graphite to temperatures between ings are usually applied to a thickness of about 100/~
2800 and 3000 C to diffuse out impurities. Chemical on particles which are on the order of 150 to 200/a
purification consists of heating graphite in the presence diameter. The primary purpose of the coating is to
of a halogen-containing gas to remove impurities as contain fission products.
volatile halide compounds. Higher purities are
attained by the more expensive chemical purification 2.3. Machining practice
method. A typical chemically purified graphite The machinability of graphite depends upon the
contains < 10 ppm Si, < 10 ppm A1, < 5 ppm Fe, raw materials used in its manufacture and upon pro-
< 10 ppm Ca, < 1 ppm Mg, < 1 ppm Ni, < 1 ppm Ti, cessing variables. Products which are processed at a
< 5 ppm V, < 1 ppm B and a maximum ash content low graphitizing temperature or which contain a
of 100 ppm. poorly graphitizing component are quite abrasive
New techniques and variations of existing proces- and cause excessive wear of machining tools. Most of
ses are being developed to produce a wide range of the common nuclear graphites can be turned, sawed,
graphite products for nuclear applications. For milled, bored, planed, drilled, shaped, ground,
example, raw-coke graphite is manufactured from an tapped, and reamed [4]. Lubricants or cutting
uncalcined "raw" petroleum coke, whereas in the fluids are normally not used, thus eliminating a
conventional process the coke is calcined prior to mix- potential source of graphite contamination. Either
ing with binder, baking, and graphitizing. In making wood-working or metal-working machines can be
raw-coke graphite, uncalcined coke and pitch used in machining graphite. However, metal-working
binder are mixed directly and are calcined in the machines are preferred because of their accuracy,
baking process. Other manufacturing techniques which versatility, and automatic features.
so far have limited applications in the nuclear field In a machining operation, graphite is crushed or
include pressure baking and hot working. fractured by the tool. The graphite chip is granular
in form and the surface is pitted when particles are
2.2.2. Pyrolytic carbon torn from the matrix. The degree of pitting depends
Pyrolytic carbon is a vapor-deposited, highly an- largely upon the grain size of the graphite and the
isotropic form of carbon in which the carbon-layer depth of the cut. Most of the machined chips are
planes are preferentially oriented parallel to the surface in the form of extremely fine grains. High-efficiency
of the substrate. Pyrolytic carbon is made by thermal dust collectors are required to remove the fine
decomposition of hydrocarbon gases [3]. The pre- powdered material. Removal of cutting dust is
ferred orientation, density and other properties can necessary because the surfaces must be clean to
be varied widely by changes in gas pressure, tempera- maintain dimensional tolerances.
ture, gas flow rate, geometry of the system, and other The finish of graphite is largely dependent upon
deposition conditions. Subsequent heat treatment to the feed and speed of cutting. The magnitude and
higher temperatures improves the crystallinity. spacing of the minute ridges and valleys produced
Large pyrolytic carbon shapes have been produced by the cutting tool determine the surface roughness.
for space applications, and pyrolytic carbon coatings Finishes of the order of 63 to 240/~ in., rms, are
for nuclear fuel particles have been developed. For readily attained. Carbide cutting tools are preferred
416 D.E. Baker, Graphite as a neutron moderator and reflector material
to high-speed tool steel tools because of their greater to itself and to metals [7]. Difficulties in graphite
resistance to wear. Failure of the tool material is pri- brazing are associated with differences in thermal ex-
marily due to wear on the cutting edge caused by the pansion coefficients of the components and with the
abrasiveness of the graphite. Tools and cutters are inability of the brazing alloys to wet and flow on
ground with a relief angle of from 15 to 20 ° and usu- graphite sufaces. An alloy of 48Ti-48Zr-4Be is suit-
ally have 0 ° rake. For a rough lathe finish, the depth able for joining graphite to itself and to molybdenum.
of the cut may be as great as 0.5 in. and the rate of The major constituents are strong carbide formers,
feed as fast as 0.1 in. per revolution [5]. For a fine and their relatively low thermal-expansion coeffi-
finish, the depth of cut varies from 0.001 to 0.01 in., cients compare favorably with that of graphite. The
and the rate of feed from 0.005 to 0.02 in. per revo- Ti-Zr-Be alloy exhibits poor resistance to corrosion
lution. A tolerance of-+ 0.002 in. can be maintained. by molten fluoride salts. An alloy of 35Au-35Ni-
Graphite can be rough cut on band saws operating at 30Mo will braze both graphite-to-graphite and
3000 fpm and having a blade 0.035 in. thick with graphite-to-metal with high integrity and will resist
0.065 in. set and 2 to 6 teeth/in. Hollow drills em- corrosion by molten fluoride salts. In both low- and
ployed with vacuum dust removal are more successful high-porosity grades of graphite, the Au-Ni-Mo
then ordinary twist drills. alloy can produce brazed joints having strengths at
Care must be exercised to avoid contaminating least as great as that of the graphite being brazed.
the graphite during machining and inspection opera-
tions. Operators are required to wear special protec- 2.5. Graphite grades and material designation
tive coveralls, gloves and caps in the shop area. Such Nuclear graphite is available in numerous grades
precautions must be taken to exclude high capture differing in grain size, strength, density, purity,
cross section impurities and corrosive contaminants piece size, processing conditions, and many other
which may be chemically incompatible with reactor characteristics. The different types of graphite are
materials. Distribution of activated contaminants usually referred to in the literature by the manufac-
throughout the reactor cooling circuit may make turer's letter or number designation and frequently
subsequent maintenance difficult [6]. are without further description. Information such
as process temperatures or raw material identifica-
2.4. Cementing and joining techniques tion which are needed to adequately characterize
The methods used for joining carbon and graphite graphite may be unavailable if proprietary aspects
parts are similar to those for joining wood [4]. of the manufacturing process are involved.
Threaded, pinned, tapered, butted, and tongued- Graphites which are procured on the basis of similar
and-groove joints have all been used in a variety of unirradiated physical properties will not necessarily
applications. Other methods of joining are to shrink- perform identically in a nuclear reactor. Irradiation
fit or press-fit the carbon or graphite part to a metal tests are usually performed on prototype material
component. prior to full scale production.
Carbon and graphite parts may be joined together Many carbon and graphite products have been
with resin-base cements. For maximum strength, the irradiated and evaluated for nuclear reactor applica-
surfaces should be machined as flat as possible. The tions. Brief descriptions of some of the materials
strength of a cemented joint increases with decreasing (some are current grades; others are not) discussed
joint thickness and, where possible, joints of 0.005 in this chapter are given in table 1. Since wide varia-
to 0.02 in. thickness are recommended. After curing tion of properties is possible for some types of
the resins, the assemblies are heated to about 900C graphite, manufacturers should be contacted for cur-
to carbonize the cement. Joints with a modulus of rent product data.
rupture of about 2000 psi are attained after carboni- The cost of nuclear graphite varies widely de-
zation of the cement. When the cement is heated pending on purity, size, shape, quantity, and physi-
to graphitizing temperatures ( > 2200 C), the strength cal properties. Currently, unmachined grades with an
is decreased by about 10 to 30%. absorption cross section of approximately 4.3 mb
Alloys have been developed for brazing graphite cost $1200 to $1500 per ton in several-hundred-ton
Table 1 graphitized over 2500C, low porosity,

Graphite material designations [ 8,91 • isotropic
HLM-85 Calcined petroleum coke and coal tar pitch,
Material Description extruded, graphitized > 2500C, 1.83
designations g/cm 3 density
AGOT Calcined petroleum coke and coal tar pitch, KC Kendall coke, Chicago pitch, extruded,
Nuclear-2 extruded, graphitized > 2500C, 1.6 to 1.7 thermally purified, anisotropic, about 1.7
R-1 g/cm3 density, 4.5 mb thermal-neutron ab- g/cm 3 density, 4.40 mb cross section
sorption cross section, B ~ 1 ppm NC7, NC8 See EGCR
AGR Calcined petroleum coke, extruded graphit- ~A The standard British moderator graphite,
ized ~ 2500C, 1.6 g/cm 3 density
1.65 to 1.75 g/cm 3 density, about 4 mb
ATJ Calcined petroleum coke and coal tar pitch, cross section
fine grain, 0.006 in. maximum grain size, TSF Similar to AGOT except gas purified, 3.5
molded, graphitized > 2500 C, impregnated, Nuclear-1 to 3.85 mb cross section
1.73 g/cm 3 density R-3
AUC Calcined petroleum coke and coal tar pitch,
TSGBF Texas-Lockport coke, standard pitch, ex-
grain size 0.01-0.03 in., extruded, graphit-
truded, graphitized and gas purified in one
ized > 2500 C, impreganted, maximum ash
step at 2450C, 1.65 g/cm3 density, 3.75
0.08% 1.68 g/cm a density
mb cross section, similar grade now design-
CSF Cleves coke, standard (Barrett No. 30 ated GBF by manufacturer
medium-hard coal tar) pitch, extruded,
TSX Fine grain needle coke, extruded, graphit-
graphitized at 2800C, gas purified, 1.66
ized at 3000C, anisotropic, 1.7 g/cm 3
g/cm a density, 3.83 mb cross section
density, 3.75 to 3.85 mb cross section
CSGBF Similar to TSGBF except manufactured
WSF Similar to CSF except made from Whiting
from Cleves coke
coke
EGCR Needle coke, coal tar pitch, extruded, 1
ZT Group of high density, recrystallized mater-
pitch impregnation, graphitized at 2800 C,
17% X 17% X 240 in. blocks, NC-7 was ials made by subjecting base materials to
prototype material, NC-8 production lot high pressure at temperatures within the
plastic range, 1.9-2.0 g/cm 3 density
H4LM Maximum particle size 0.033 in., molded,
impregnated, 1.72 g/cm 3 density ZTA Maximum grain size 0.006 in., hot-worked,
highly anisotropic, 1.95 g/cm3 density,
JOZ Manufactured from uncalcined petroleum ash <0.25 w/o
coke and coal tar pitch, fine grain, molded,
quantities. Machining adds $700 to $1200 per ton. where the carbon atoms are directly superimposed
Higher purity graphite with a cross section of approx- over each other in alternate layers. A less common
imately 3.8 mb requires additional processing which form is the rhombohedral structure, in which the layer
adds $200 to $400 per ton to the total cost. Unpuri- planes have an ABCABC... stacking sequence. Two
fled gas-baked carbons for reactor shielding applica- important structural features that account for many
tions cost about $500 per ton, unmachined, in multi- of the unique properties of graphite are: 1) the sys-
ton quantities. tem of strong chemical bonds forming large
sheets of hexogonal rings in which the electrons are
quite mobile and 2) the large spacing between carbon
3. Physical properties layer planes [10]. The bond structure gives the
graphite crystal metallic properties in the a direction
3.1. S t r u c t u r e and non-metallic properties in the c direction. The
The hexagonal crystal structure of graphite, which structure accounts for the high thermal and electrical
is the most common form, is shown in fig. 2. The conductivities in the a direction and the low conduc-
layer planes form a stacking sequence ABAB .... tivities in the c direction. The forces between atoms
41 8 D.E. Baker, Graphite as a neutron moderator and reflector material
A u ~o_~ ¢.9
Unit Cell:.
a - Z . ~ I 2 t-IX 0601 h
5 - LR2_a 6,8
¢ • 6 . / 0 ~ . + n 0007 A
V o l u m - 35.1t0 A3
A i m s Per Unit Cell - 4
6.7
A
6.6 • l J q I ~ I I I
0 2OO ~ Ca} 80O Z000
T~nwiture. C
Fig. 3. Change in interlayer spacing of graphite with tempera-

Fig. 2. Crystal structure of graphite [10]. ture [10].
in a layer plane are due to strong C-C chemical bonds, neutron absorption cross section and high scattering
whereas the forces between layer planes are relatively cross section. Nuclear graphite has been produced in
weak. large quantities with an absorption cross section of
CrystaUites in which atoms are arranged in a charac- 3.8 rob. Because typical impurities in graphite have a
teristic, periodic array typically vary in size from 300 greater cross section for absorbing neutrons than
to > 1000 A in the a direction. The unit cell dimen- carbon, it is desirable to minimize impurities.
sions of graphite are derived from analysis of X-ray Elements that commonly contribute to an increase
diffraction data. The change in interlayer spacing with in the absorption cross section of graphite include
temperature is shown in fig. 3. Between 0 and 800 C, the following: H, B, N, C1, Ti, V, Gd, and other rare
the average coefficient of thermal expansion for earth elements. Graphite containing several percent
single crystals in the c direction is 28.3 × 10-6 C-1 . boron may be used as a combined moderator and
Changes in the a unit cell dimension are smaller, that neutron absorber in the shielding structure of
is, the thermal expansion coefficient is nuclear reactors. For example, shielding in the Fermi
-1.5 X 10 -6 C-1 over the range from 0 to 150C and reactor consists of boronated graphite containing
+ 0 . 9 X 1046 C -1 from 600 to 800C [11]. 7 w/o boron as B4C particles.
Pyrolytic carbon has a structure that distinguishes Absorbed water and nitrogen in the pores of
it from electrographite. Pyrolytic carbon is deposited graphite have a negligible effect on the moderating
with the layer planes parallel to the substrate surface properties [12]. For example, 0.015 w/o water in-
but randomly oriented in the a-axis direction. The creases the slowing down power about 1%. The
structure resulting from the disordered layer planes is slowing down power is the average logarithmic energy
described as "turbostratic". Stress annealing, e.g., change of a neutron when it collides with a modera-
compressing to about 5000 psi at > 2800 C, tor atom divided by the mean free path between
straightens the planes and produces a material with collisions. For nuclear graphite with a density of
properties which approximate those of a single 1.60 g/cm 3 , the slowing down power is 0.060 cm -1 .
crystal of graphite.
Typical densities of pyrolytic carbon and other car- 3.3. Thermal properties
bon products are compared in table 2. 3.3.1. Phase diagram of carbon
The phase diagram of carbon, shown in fig. 4, in-
3.2. Nuclear properties dicates that the melting point of graphite is 4250 K at
The desirable nuclear characteristics of graphite as 103 atm. The melting point curve and vaporization
a moderator and reflector material are its low thermal characteristics of carbon have not been firmly estab-
Table 2 Table 3
Typical densities of carbon and graphite products. Vaporization data for carbon [20].
Material Bulk density, g/cm 3 Temperature, K Pressure, atm
Pyrolytic carbon 1.2-2.2 2000 1.31 X 10-l°

Single crystals (theoretical density) 2.26 2500 1.05 X 10-6
Nuclear graphite-moderator and reflector 1.5-1.7 3000 5.38 X 10.-4
Porous electrocarbons and graphites 0.6-1.3 3500 5.30 X 10-2
Carbon felt 0.08-0.17 3800 1.0
lished because of experimental difficulties at very high about 2500 K. Vapor pressure data for temperatures
temperatures and pressures. Both monatomic and above 3000 K are not in good agreement and should
polyatomic species of carbon result from the vapori- be regarded as tentative. Vaporization data for car-
zation of graphite. Mass-spectrometer measurements bon are given in table 3.
indicate the presence of the molecular species C 1
through C 5 , and higher molecular clusters are predicted 3.3.2 Specific heat
in the vapor [13]. There seems to be general agree- The thermodynamic properties of graphite at low
ment on a value of 170 kcal/mole for the heat of sub- temperatures are given in table 4 [15]. The usual
limation of carbon atoms. symbols for specific heat at constant pressure (Cp),
The vapor pressure of carbon is negligible up to standard enthalpy (H°), entropy (S°), and free energy
(F °) are used. The specific heat of graphite can be
described by a quadratic function of temperature
1000 from 13 to 50K [8]. From 50to a b o u t 6 0 0 K , C p
increases approximately linearly with temperature.
Thermodynamic properties of graphite above room
temperature are given in table 5 [16]. Heat capacity
800
data between 298 and 1500 K are represented by the
equation:
Cp = -1.265 + 14.008 × 10-3 T - 103.31
E 600
X 10- T T 2 + 2 . 7 5 1 X 10- g T 3 ,
Grq~lte
where T is the temperature in degrees Kelvin and Cp
400 is the heat capacity in cal/mole-K [ 17]. Within the
accuracy of the measurements, the specific heat of
iqukJ all coke-based artificial graphites is the same at all
temperatures above a few degrees absolute [18].
3.3.3. Thermal conductivity

The thermal conductivity of carbon products at
~.~""'~J Gas about 25 C varies from the extremely high value of
0 i
3800 4000 42110 4400
3.8 cal/sec-cm-C for pyrolytic graphite in the layer
plane direction [19] to the low value of 8.6 X 10-s
Temperature, K
cal/sec-cm-C for insulating carbon felt [20]. The
thermal conductivity of nuclear graphite lies between
Fig. 4. The phase diagram of carbon [8,14,20]. The triple
point occurs at 103 atm and 4250 K and the sublimation point the extremes and usually ranges from about 0.15 to
occurs near 3800 K. 0.4 cal/sec-cm-C at 25 C. The conduction of heat in
420 DE. Baker, Graphite as a neutron moderator and reflector material
Table 4
Thermodynamic properties of graphite at low temperatures [ 151 .
Temperature (T), Cp, H To - H oo S°

-(F~-Ho)/T
K cal/mole-K cal/mole cal/mole-K cal/mole-K
13 0.0080 0.0421 0.0041 0.0009

15 0.0102 0.0592 0.0056 0.0017
25 0.0300 0.2478 0.0154 0.0055
50 0.1210 2.0226 0.0629 0.0225
75 0.2501 6.5963 0.1346 0.0467
100 0.3963 14.674 0.2275 0.0807
125 0.5723 26.714 0.3346 0.1209
150 0.7718 43.456 0.4563 0.1666
175 0.9804 65.339 0.5925 0.2192
200 1.180 92.460 0.7384 0.2761
225 1.461 124.895 0.8916 0.3365
250 1.629 162.846 1.0510 0.3995
275 1.843 206.232 1.2157 0.4658
298.16 2.038 251.183 1.3718 0.5294
300 2.053 254.946 1.3846 0.5348
Table 5
Thermodynamic properties of graphite above room temperature [16].
o o
H298 - H0 = 251 cal/mole
o o o -(F~ o
Temperature (T), C p, H T - H298, S T, -H298)/T,
K cal/mole-K cal/mole cal/mole-K cal/mole-K
298 2.07 0 1.37 1.37

300 2.08 4 1.38 1.37
400 2.85 251 2.09 1.47
500 3.50 569 2.80 1.67
600 4.03 947 3.49 1.92
700 4.43 1,370 4.14 2.19
800 4.75 1,830 4.75 2.47
900 4.98 2,318 5.33 2.76
1000 5.14 2,823 5.86 3.04
1100 5.27 3,344 6.35 3.31
1200 5.42 3,874 6.82 3.60
1300 5.57 4,428 7.26 3.86
1400 5.67 4,990 7.67 4.11
1500 5.76 5,562 8.07 4.37
1600 5.83 6,142 8.44 4.61
1700 5.90 6.728 8.80 4.85
1800 5.95 7,320 9.14 5.08
1900 6.00 7,918 9.46 5.30
2000 6.05 8,520 9.77 5.51
2100 6.10 9,133 10.07 5.73
2200 6.14 9,745 10.35 5.93
2300 6.18 10,360 10.63 6.13
2400 6.22 10,980 10.89 6.32
2500 6,26 11,600 11.14 6.50
2600 6.30 12,230 11.39 6.69
2700 6.33 12,860 11.63 6.87
2800 6.36 13,500 11.86 7.04
2900 6.39 14,140 12.08 7.21
3000 6.42 14,780 12.30 7,38
3500 7.46 18,100 13.30 8.13
3000 C is shown in figs. 8 and 9, which illustrate that

0.6
the thermal conductivity parallel to the deposition
plane is two orders of magnitude greater than that in
0.5
the perpendicular direction.
3.3.4. Thermal expansion

0.4
The thermal expansion of graphite reflects the net
influence of thermal vibrations of the lattice atoms,
the elastic properties of the crystallites, and the details
of bonding [22]. Since the graphite crystallite is ex-
O.2 tremely anisotropic, thermal expansions are quite dif-
ferent in directions perpendicular and parallel to the
layer planes. The coefficients of thermal expansion
(CTE) of polycrystalline graphites and graphite single
I
0
-~0
I
-ICO 0
I i
100
i
~0 ~
i
400
i
~00
i
crystals are shown in figs. 10 and 11. A few of the pro-
600
TemRraurL C
cess variables that affect the CTE are coke particle size,
pitch impregnation, and calcination and graphitization
Fig. 5. Thermal conductivity of TSX graphite. (Submitted by temperatures. Fig. 12 shows the variation of CTE in
Pacific Northwest Laboratory, 1 November 1968). various graphites measured from room temperature
to 1000C as a function of the bulk density. The
polycrystalline graphite occurs mainly by lattice vibra- CTE varies over a wide range, but the change in CTE
tions or phonon waves, with negligible electronic con- with temperature is approximately the same for all
tributions. The maximum conductivity of nuclear graphites. It has been found empirically [20] that
graphite typically occurs below room temperature [8], the mean CTE from 20 C to a final higher tempera-
as shown in fig. 5. The thermal conductivity decreases ture can be obtained by adding the factors shown in
at elevated temperatures as shown in fig. 6, and is table 6 to the value for the temperature interval 20
highly dependent on the type of material and proces- to 100C. The CTE from 20 to 100C for KC graphite
sing variables. Fig. 7 shows the dependence of thermal is 1.5 X 10-6/C in the parallel direction and
conductivity on the heat-treatment temperature for 4.6 X 10-6/C in the transverse direction. Values for
an experimental Texas-coke graphite. The extreme AT J, which is more isotropic than KC, are
anisotropy of pyrolytic carbon which was annealed at 2.2 X 10-6/C in the parallel direction and
3.4 X 10-6/C in the transverse direction.
• Flash Dlffuslvity MNsurments

• Series C0mpari~n Musuremer~s
~ k Walt • RmdH
ai l~RFI0wMasurments
i 1.6 s/cm.C"A"~T'rg
460 + O.28 a=
0.29
0.8 O.19
- ~ 9 • °i~ .o. - a-
0.4 O.10
0 I I i i i i
o ~oo 1ooo 15oo 20o0 25oo
Tomm
lm
' turC
o.
Fig. 6. The thermal conductivity of ZTA graphite perpendicular to the pressing direction [ 21 ].
422 D.L: Baker, Graphite as a neutron moderator and reflector material
0.16 _ ~ Healrrmtmnt
~ ~ Temperature
0.12
E
2~0C
0.06
J 21110C
0.04
1800 C
L t I I
100 ZOO 300 400 ~0
TestTempmlture,C
Fig. 7. Dependence of transverse thermal conductivity for an experimental graphite on heat-treatment temperature. (Submitted by
Pacific Northwest Laboratory, 1 November 1968).
10.0
8.0
O.Oe
l 0.3
6.0
0.2
| 4.0
|
0.1
0.~
IO
2.0
i i I I i 0 i I i I 0
29O 40O ~0 8OO 1000 1000 1210
Temperature,K Temperature.K
Fig. 8. Thermal conductivity of Pyrolytic carbon parallel to the Fig. 9. Thermal conductivity of Pyrolytic carbon transverse to
deposition plane [19]. the deposition plane [19].
80
Memsurld /
/
~ Extrapolated / ManufacturM Graphites
/
,e (With Grain) .~
400 60
/
,t
" SingleCryStal m
o
,,"/ c - Direction
32O c
40
s
z
"5
20
I
I
I
/
I f Single CryStal
I ...a
I
I Manufactured Griphltes
I Musurod
(Across Grain)
) ~ Extrapolated
i
/
0 ~ I , I , I , I •40 I , I , I , I t
-27~ 0 800 1600 2400 32110
-2T) 0 800 1600 2400 3200
Temlpalture, C
TemPerature. C
Fig. 10. Thermal expansion of graphite [22]. Fig. 11. Thermal expansion of graphite [ 22].
3.3.5. Emissivity
The emissivity of graphite is an important charac-
teristic in studies of radiant heat transfer and in mea-
Type of Graphite
surements of graphite surface temperatures by
o Pyrolytic
optical pyrometry. The emissivity of graphite varies
: /"
a Grade ZT
with the surface finish, and prolonged heating of a
polished surface at high temperatures will change the
character of the surface and increase its emissivity
[2]. A general conclusion from the available data is
that the spectral emissivity of graphite at 0.655 p
lies between 0.75 and 0.90, with the exact value de-
pending on the nature of the surface and to a lesser
extent on the temperature. The importance of the
surface condition on the spectral and integrated emis-
111} sivity is indicated in table 7.
3.4. Electrical properties

e ' ~ . c l . . ~ ~ Grain The electrical resistivities of extruded nuclear
_ | I I'l graphite at 25 C range from 350 to 600/aohm-in. in
1.7 1.9 2.1 2.3 the direction transverse to the extrusion axis and
Density. ~cm 3 from 200 to 400 pohm-in, in the parallel direction.
The electrical resistivity of type AGR graphite as a
Fig. 12. Thermal expansion of various graphites versus density function of temperature is shown in fig. 13. The im-
(Average 25 C to 1000 C) [ 23]. portance of raw materials is emphasized by the fact
424 D.E. Baker, Graphite a~ a neutron moderator and reflector material
Table 6
Factors for calculation of mean coefficient of thermal expan-
sion [20].
Final Term to be added to CTE

temperature, C determined over temperature
range 20 to 100C, 10-7/C
100 0
200 2.0 ¢
300 4.0
400 6.0
500 7.7
600 9.2
700 10.4 I , I [ J I
800 l 1.4
900 12.3 T~Wtslurl C
1000 13.2
1500 17.2
2000 21.2 Fig. 13. Electrical resistivity of extruded grade AGR graphite
2500 25.2 [25].
Table 7
Emissivity of type AUC graphite [24].
Emissivity = a + 10-5 bT where T is the absolute temperature, K, and a and b are constants.
Spectral Integrated emissivity

emissivity
(h = 0.665 u) (0.2 to 3.5p) (0.2 to 10p)
Surface treatment a b a b a b
Polished 0.803 -0.249 0.495 12.2 0.448 13.8

320 Grit 0.849 -2.38 0.547 11.4 0.504 11.9
180 Grit 0.896 -2.71 0.663 8.81 0.598 9.32
80 Grit
0.962 -3.96 0.668 7.89 0.647 7.76
Oxidized and
lightly sandblasted 0.975 -4.03 0.768 4.16 0.732 5.21
that the resistivity of graphite made from lampblack is 3.5. Mechanical properties
about 5 times the resistivity of graphite made from 3.5.1. Tensile strength
petroleum coke. The coke calcination temperature Unlike most materials, graphite increases in
and m a x i m u m heat-treatment temperature also affect strength with temperature. Its strength reaches a max-
the resistivity of the final product. Resistivity values imum at about 2500C as shown in fig. 14. The
can be used to indicate the relative crystalline perfec- tensile strength of H4LM graphite at liquid-hydrogen
tion and degree of orientation in a material. The elec- ( - 2 5 3 C) and liquid-nitrogen ( - 1 9 6 C) temperatures
trical resistivity of highly anisotropic pyrolytic carbon is the same as the room-temperature value [28]. Be-
at 25 C is 4.6 × 10-4 ohm-cm in the a or layer plane cause graphite has a low density, its strength-to-
direction and 0.48 ohm-cm in the c direction [26]. weight ratio is better than that of other materials
3.0 LO
~ s ParalltoelGrain/
i .c
2.0
6
e~
PWlmndlculgr ~o Griln
Is. 4
L0
~pwpendicular To Grain 2
i i ~ , i i i
00 i
500
i
1000
,
1500
- -
2OO0 25OO 3006
, i
Temp~tture. C Tempw~'uCre,
Fig. 14. Tensile strength of H4LMgraphite [27]. Fig. 15. The ultimate compressivestrength of H4LMgraphite
[27].
above about 1500 C. Graphite strength is influenced
by such variables as density, orientation, particle size,
types of coke and pitch, and processing temperatures. 6.0
The strength of graphite is higher in the direction

parallel to the layer planes. In general, the tensile 5.0
strengths of nuclear graphites at 25 C fall in the 1000 i
to 3000 psi range parallel to the layer planes and
800 to 1500 psi across the layer planes. Adsorbed
gases influence the strength of graphite at high tem- i 3.0
peratures. Increases in strength of up to 30% have

been observed under high-vacuum conditions, as com-
pared with strengths measured in air or hydrogen
LO
[29,30]. The ultimate tensile strength of pyrolytic
graphite parallel to the basal planes is about 15,000
psi at 30 C. Hot working pyrolytic graphite, "~ 20%
,
]0
I ~
20
t *
30
I ,i
at 2760 C, increased the room temperature ultimate Oxit~tlon,
strength from 25,800 to 81,700 psi [31], A 50% re-

duction in tensile strength occurs in a nuclear Fig. 16. Compressivestrength of PGA graphite as a function
graphite after approximately 7% oxidation by of oxidation [ 34].
CO 2 [32].
3.5.2. Compressive strength strength of pile grade A graphite on the extent of oxi-
The ultimate compressive strength of graphite dation is shown in fig. 16.
ranges from 4000 to 10,000 psi and is not strongly
dependent on the direction of applied force [8,33]. 3.5.3. Young's modulus
Compressive strength also increased with increasing Young's modulus of elasticity is a measure of the
temperatures in a manner similar to tensile strength as resistance to tensile or compressive strain of a mater-
shown in fig. 15. The ultimate compressive strength ial under stress. Average room-temperature Young's
of pyrolytic carbon at 25 C is 14,000 psi in the moduli for nuclear graphites range from 0.7 to
basal plane direction and 68,000 psi in the c direction 1.5 X 106 psi in the parallel direction and from 0.6
[26]. The dependence of the ultimate compressive to 1.2 × 106 psi in the transverse direction. Young's
2.0
ATJ
100 o PyrolyticCarbon
o SingleCrystal, c Axis
g
-5 o SingleCrystal, a Axis
|
Q.
L0 ~ ~ - v,"
_.=
•~ . ..... , I , , , , I . , . L I . . . . I . . . . I , ,
Alona ~,rain
500 )000 1500 2000 2500
Temperllurt, C
1.0
Fig. 17. Young's modulus for H4LM graphite [35[.
Across Grain
modulus increases with temperature as shown in fig.
17. Young's modulus for pyrolytic graphite at 25 C
along the a-axis approaches 107 psi as shown in fig. 0. I ~ I I i
1.7 1.q 2.1 2.3
18, which relates Young's modulus to the bulk density.
These moduli were all obtained by resonant frequency Density, g/cm3
measurements in the sonic range. A comparison of Fig. 18. Sonic Young's modulus for various graphites versus
sonic with static measurement of Young's modulus density [23].
in AUC graphite at room temperature showed agree-
ment within 4% [35].
Temperlture, C
3.5.4. Creep at high temperature [20]
~eo 23oo
Graphite is not perfectly elastic, even at room I 1 I I
temperature, and yields plastically under stress. The
stress-strain curves for graphite are not linear, and 10"3 ~r~ ~1
there is a residual strain in the material after stressing.
This plastic straining at low temperatures is not
considered to be creep. Creep in graphite is ob-
served at temperatures above approximately 1700 C,
while creep in carbon has been observed at 1000 C.
Although carbon products may be stronger than
graphite at room temperature, they creep more 10.4
easily at high temperatures. Creep in graphite is de-

pendent on many variables, including grain orienta-
tion, density, and processing conditions. Graphites
having a high degree of anisotropy are more resistant
to creep and display less creep with the grain than
against the grain. The temperature dependence of the 10"5 i , ] i
steady-state creep rate of ATJ graphite oriented 3.0 3.4 ~S 4.2
with the grain is shown in fig. 19. An activation ener-
gy of 124 kcal/mole for the creep process was cal-
culated from these data.
Fig. 19. Tensile creep of ATJ graphite parallel to the grain
[20].
3.5.5. Coefficient of friction at liquid-nitrogen temperatures. Surface areas calcul-

The coefficient of friction (/a) is defined as: ated from these measurements are called BET sur-
# = f/F where f is the force necessary to either start face areas. BET surface areas depend on the outgas-
(static) or maintain (dynamic) the motion, and F is the sing temperature in the range 100 to 500 C. The out-
force with which the two surfaces are pressed together gassing temperature influences the amount of residual
normal to the direction of motion. The coefficients gas which can cover sites capable of adsorbing
of friction for several types of graphite with various nitrogen. BET surface areas of several types of
surfaces are given in table 8 [20,33]. The following graphite and carbon are given in table 9.
generalizations can be made: 1) static friction is The pore size distribution is determined from
always higher than dynamic friction; 2) surface nitrogen desorption data and mercury porosimetry.
finish and condition have the most pronounced effect The bulk volume of AGOT graphite consists of 22%
on friction; 3) the coefficients of friction are approxi- accessible void volume and 4% inaccessible void
mately independent of the force, stress and orienta- volume [36]. The distribution of pores in the acces-
tion of the graphite; 4) the static coefficient of fric- sible void volume of AGOT graphite is as follows:
tion increases as the temperature rises, whereas the 13% greater than 14/a radius, 64% from 0.05 to 14/~,
dynamic coefficient is only slightly affected; 5) the and 23% less than 0.05/a. The pore size distribution
coefficient of friction depends upon the gas atmos- may be modified markedly by impregnation with
phere since adsorbed gases promote slip across the sur- resins and other materials to block the pores.
faces,
3.6.2. Water adsorption and gas desorption
3.6. Surface properties and permeability Chemisorbed and physically adsorbed gases are
3.6.1. Surface area and porosimetry contained in the extensive pore system of nuclear
The specific surface area of pure, nuclear-grade graphite. Water which is physically adsorbed on
graphites is usually less than 1 m2/g [8]. The surface graphite can be removed by evacuating at room
area is normally measured by using nitrogen or temperature. Chemisorbed water reacts with
krypton gas as the adsorbate and making pressure- graphite at high temperatures and is removed as H 2
time observations in a closed system to determine and CO. The amount of adsorbed water depends on
the volume of gas adsorbed as a monomolecular layer the relative saturation pressure (P/Po), P being the
Table 8
Coefficients of friction for several graphites [ 20,33].
Material Test Atmosphere Coefficient of friction

temperature, C
Static Dynamic
ATJ on ATJ 25 Air 0.33 0.24
ATJ on ATJ 2450 Helium 0.70 0.28
H4LM on H4LM 25 Air 0.34 0.26
H4LM on H4LM 2450 Helium 0.48 0.27
ATJ on H4LM 25 Air 0.33 0.26
ATJ on polished steel 25 Air 0.35
AGOT on AGOT 25 Air 0.24
AGOT on AGOT 900 Nitrogen 0.12
AGOT on 18-8
stainless steel 204 Air 0.35
AGOT on cold-
rolled steel 204 Carbon 0.24
dioxide
428 D.E. Baker. (;raphite as a neutron moderator and reflector material
Table 9 Gases other than water vapor or the gaseous pro-

BET nitrogen surface areas [8]. ducts of the reaction between graphite and water are
evolved when graphite is heated. These gases are pro-
Carbon or graphite Outgassing Surface
bably held by chemisorption or are trapped in pores
temperature, C area, m2/g *
during cooling from graphitization. Metallic carbide
CSF 200 0.32 impurities react with moisture to produce gases not
CSGBF 550 0.36 originally present in graphite. For example, CaC 2
KC 500 0.53 hydrolyzes to Ca(OH) 2 in the presence of moist air,
WSF 500 0.87
and then partially converts to CaCO 3 in contact with
TSX 400 0.46
CSF ('( 170U powder) 500 6.70 CO 2 [20]. Desorption data for several nuclear
Furnace black 250 27.0 graphites are given in table 10. Examination of these
data leads to the following observations: [38] 1) the
* Molecular area for nitrogen assumed to be 16.2A 2. volume and composition of the desorbate obtained
at any given temperature varies for different grades
of graphite; 2) thermal or gas purification of graphite
reduces the volume of adsorbed gas; 3) temperatures
of 1800 to 2000 C or higher are required, in most
N~jen SurfaceAtu • 1.2 m2~ I I instances, to effect an essentially complete removal
of the adsorbed gas.
II
0.06 Bind ~ncludesPol~s for:
il. Solidand HollowCyltndlrs 314 In. to 1-1/2 In.
3.6.3. Permeability
D. Ms~Mion and O e s ~ Runs
~. TwoAnalytical TIchnigues The most common method of reducing the gas
0.04 permeability o f graphite is impregnation with a
carbonaceous liquid, followed by heating to carbon-
ize the impregnant [8]. Although the methods are
similar to those used to increase the density, the im-
pregnating liquid is different. Conventional pitch
impregnents increase the density without markedly
0 reducing the permeability. Impregnants with low
0 0.2 0.4 n6 0.8 LO
viscosities and greater wetting ability are more effec-
RetatlveSatuflltion PteSsurL I~ o
tive in blocking the pores and reducing the permea-
bility. Multiple impregnations are common, the num-
Fig. 20. The equilibrium amount of water adsorbed on nuclear ber depending on the size and shape of the piece,
graphite at 25 C versus the relative saturation pressure, P/Po, pore structure, and impregnant used. The permea-
where p is the vapor pressure at which adsorption takes place bility of untreated graphite base stock is about
and Po is the saturation vapor pressure of water at 25 C [37].
10-1 to 10-2 cm2/sec. Multiple impregnations with
a furfuryl alcohol impregnant decrease the per-
vapor pressure at which adsorption takes place and Po meability of HLM-85 graphite to the order of
being the saturation vapor pressure of water at 25 C. 10-s cm 2/sec [39]. Since the low-permeability
The equilibrium amount of water adsorbed on HEM-85 graphite is heated above 2650 C in the pro-
graphite is shown in fig. 20. The rate of water adsorp- cess, it is suitable for high-temperature applications,
tion is affected by the presence o f other atmospheric whereas materials processed at temperatures less
gases, such as nitrogen, oxygen, and carbon dioxide than 1200 C to carbonize the impregnant undergo
and also by the size o f the specimen. Extrapolation of further changes on heating to higher temperatures.
results from small samples to a cylindrical block of Another method of reducing the permeability of
8.2 in. diam by 29 in. long indicates that the half- graphite is by the thermal decomposition of hydro-
saturation value would be obtained in 27 hr at carbons in the pores [40]. This process, which is
P/Po = 0.82 and 4.5 days at P/Po = 0.9 [8]. similar to that used in forming pyrolytic carbon
Table 10
Volume and composition of gas evolved by various graphites [38].
Graphite Gas evolved to 1000 C, Gas evolved to 1800C, Constituents, v/o

cm 3 STP/100 cm a graphite cm 3 STP/100 cm 3 graphite
H2 Hydrocarbons H20 CO2 CO N2
AGOT 33.1 32 7 8 25 27 2
85 40 * * * 57 2
ECGR 14.5 28 7 7 4 50 4
47 38 * * * 58 2
TSX 6.9 63 6 9 2 17 3
31 53 * * * 42 3
* 0.1 to 1% if the temperature is raised rapidly, larger amounts for slow temperature rise.
coatings, reduces the permeability to gases by a factor

o f 106 to 107 near the surface.
it
4. Radiation effects 6
4
4.1. D i m e n s i o n a l changes 4
Irradiation effects have been investigated in many

kinds o f graphite over a wide range o f temperatures
! 2
and fluences. Most nuclear graphites are formed by ex- 0

trusion, and the anisotropy o f the finished graphite
results in different radiation-induced changes parallel ..-2
and transverse to the axis o f extrusion. Dimensional

-4 i i I i
changes depend strongly on irradiation temperature 4 8 12 15
and fluence *. Data on the dimensional stability o f N4tutron Fluence. 1020Neutrons/era2 (E >0.18 Me~ )
three extruded nuclear graphites irradiated near room
temperature are shown in fig. 21 and are an extension Fig. 21. Dimensional changes of extruded nuclear graphites
of previously reported data [41,42]. caused by irradiation at 30C. (Submitted by Pacific North-
When graphite is irradiated above 300 C, the re- west Laboratory, 1 November 1968).
lationship between dimensional changes and fluence
is complex [43]. A large number o f graphite irra- until turnaround and then begins to expand rapidly.
diations have been conducted in the temperature Turnaround occurs much later in the parallel direc-
range of 300 to 1200 C and up to fluences o f tion than in the transverse direction. In the tempera-
2.1 X 1022 n/cm 2 . Expansion is the ultimate ture range o f 300 to 800C, the contraction rate for
behavior for small samples at high fluences and high both orientations decreases as the temperature in-
temperatures [44]. In the transverse direction, ex- creases. The turnaround is reached at different
truded nuclear graphite expands slightly, contracts, fluences for different irradiation temperatures. At
goes through a turnaround or reversal in direction o f temperatures above 800 C, graphites initially contract
length change and then expands very rapidly [45]. more rapidly than in the 300 to 800 C range, reach
In the parallel direction, graphite generally contracts turnaround at generally lower fluences, and then ex-
* All neutron fluences reported in this chapter are of neu- pand very rapidly.
trons having energies greater than 0.18 MeV unless other- Graphites which show the least contraction are
wise noted. usually well graphitized, highly crystalline, isotropic
430 D.E. Baker. Graphite as a neutron moderator and reflector material
16.0.
ts~. ~ 7/
I
~'.4'75 C t
5.0
/ d
/ T/.~I~ C
4.0
1000-101'5C I
3.0
I
, /
lit , /
~o I ~ I * I
0 8 16
//I ,/!'/'/'/
Fast Neutron Fluenc~ 1021 Na.rh'ons/cm2 OE>O.18Mev)
LO
Fig. 23. Radiation-inducedlength changes of CSF (parallel)

// , / / ,**.,,, c graphite for several irradiation temperature ranges [45].
0 I/ / //
-kO
Iilm"UPJC ~ ' " - - Y

II~'II'T~ C
t i I I I i l i I
15.0
1
l
.2.00 4 8 ll 16 aO 14 28
l000-1015 C
5.0
Fig. 22. Radiation-induced length changes of CSF (transverse)

graphite for severalirradiation temperature ranges [45]. 4,0
materials having a high CTE. However, the properties

3.0
which minimize contraction may tend to augment 650-750 C /
the ultimate expansion. It is possible that for high-
fluence, high-temperature use, the ultimate expansion
phase for well graphitized, crystalline, isotropic
! •0
/
/
graphites with low thermal expansion coefficients
may be delayed to higher fluences [45].
/
Dimensional stability data for CSF graphite are pre-
sented in figs. 22 and 23, and corresponding data for /
NC8 graphite, and anisotropic needle-coke material, ° ~,,~L / /
L,t\-..~.,.~/' ,,,-. c
/
,/¢,oo-,,, c
are shown in figs. 24 and 25. Data for the less
graphitic TSGBF material are shown in figs. 26 and
27. Comparison of the TSGBF data with those for ot oc
the other graphites indicates that materials must be
-2.0 1100-UT.SC
well graphitized to achieve dimensional stability.
0 4 8 12 16 20
The effect of irradiation on the apparent crystallite
Fast Neutron Fluenc¢ 1021Noutrons/cm 2 (E >0,18 Mev)
size of CSF graphite in the c direction, Lc, is shown
in fig. 28. The rapid radiation-induced contraction
of Lc by approximately 75% occurs with other
nuclear graphites as well [46]. Fig. 24. Radiation-induced length changes of NC8 (transverse)
graphite for several irradiation temperature ranges [45].
925-975 C'---'J
~.0
¢0
T ,
~-~o c
7.5
2.0
50O-55OC
J
0 3.0
~ llO0-1175C
-2.0
< /
~ 2.0
/ ,,i 775-825C
5
1.0 /, !
~0
q~Mr~-g75C 400.475C " ~ ' ~ . . ~ / / i
-&O
~0-750 C / /
I[ /"
I I I I I I
-10. 0 -LO
4 $ 12 16 20 24
I ~0-5~ C
FastNeutron Fluefct 1021 Neutronl/cm 2 (E >(118 Mev~
400-475C
-2,0
Fig. 25. Radiation-induced length changes of NC8 (parallel) O 4 8 12 16 20 24
graphite for several irradiation temperature ranges [45].
Fast NeutronFluence, 1021Neutrons/cm2 (£ >0.18 May)
The irradiation behavior of over 50 different Fig. 26. Radiation-induced length changes of TSGBF (trans-
grades of graphite is summarized in figs. 29 and 30. verse graphite for several irradiation temperature ranges [45].
The spectrum of graphites represents a wide variety of
cokes, binders and processing conditions. The data are
grouped into two bands representing irradiation
temperature ranges of 400 to 825 C and 850 to
1275 C. The unbounded region on the right side of
the band in fig. 30 indicates that not all parallel
t .-.c/ !
samples have reached turnaround. However, many '°F.,.c /!.--c
parallel samples have turned around within the
shaded area, and the others are expected to turn
around at higher fluences [47]. There are exceptions 1260-1TI~;C
to the trends in figs. 29 and 30 such as the improved
isotropic graphites where it appears that rapid expan-
sion may be delayed to higher fluences.
The basic damage mechanism causing the ob-
served changes is believed to be the c axis expansion
as influenced by crack closure before turnaround,
crack generation after turnaround, and creep of the
materials [45]. The dimensional stability may be 0 8 16
different for large blocks and small samples [49]. FastNeutron Fluence. 102] Neutrons/cm2 (E>0.18 Mev)
The dimensions of samples for the irradiation studies Fig. 27. Radiation-induced length changes of TSGBF (parallel)
were generally less than ~ in. diam and 4 in. long. graphite for several irradiation temperature ranges [45 ].
432 D,E. Baker, (;raphite as a neutron moderator and re~lector material
600 12.0
50O 8,0
4.0
!
0
t.>
~' -4. 0
200 ~ \ , ~
-8.0
-12.0
0 4 8 12 16
Fast Neutron Fluence, 1021NlutronlJcm2 (E >0,18 Mev)
0 8 16 24 )2
Fig. 28. Effects of irradiation at various temperatures on appa- Fast Neutron Fluence, 1021Neutrons/cm2 (E>0. 18 Mev)
rent crystallite size, Lc of CSF graphite [45].
Fig. 30. Radiation-induced dimensional changes of graphite
in the parallel direction [48].
6.0
4.2. Electrical and thermal property changes
4.2.1. Electrical resistivity
In contrast to most other properties, the electrical
resistivity increases rapidly by 100 to 200% at very
low neutron fluences, as shown in fig. 31. It then
generally levels off at about 35 to 40 X 10-4 ohm-cm
in the transverse direction and 20 to 25 X 10-4
ca 2.0
ohm-cm in the parallel direction until after turn-
around has been passed in the dimensional behavior.
When graphite begins to expand after turnaround,
0 the electrical resistivity again increases and continues
to do so with increasing irradiation. Radiation-in-
duced changes in electrical resistivity are generally in-
-2.0 dependent of irradiation temperature and type of
nuclear graphite.
0 8 16 24 32
Fast Neutron Fluence. 1021 NeutronS/era2 (E >0.18 Mev) 4.2.2. Coefficient of thermal expansion
Fig. 29. Radiation-induced dimensional changes of graphite in Radiation-induced changes in the mean coefficient
the transverse direction [48]. of thermal expansion (CTE) from 25 to 425 C as a
function of neutron fluence are shown in fig. 32. In
However, it appears that expansion will ultimately be both orientations CSF graphite shows only slight
the controlling behavior in large blocks also. The changes in CTE below fluences of about 1.0 X 1022
dimensional stability data presented in this section in- n/cm 2. The CTE increases at higher fluences after the
dicate the importance of selecting well characterized turnaround in dimensional behavior. Although most
graphites for nuclear applications.
70
--I/
50
E
Y
E
~0
n 4 o ~ r~
.f
Y Irrldlallon Fluence,
~0 E Trap.C 1021Neutrons/cm2
f t 0.~
NC8II .... 0
parallel e
0.29 NOIJ- .... 0

ZO |
0.20
3.41
(110
0 , I , I , I , I t 14. ]5
0 4 8 12 16 20
Fast Neutron Fluencl, 1021Ntutrons/cm2 (t>O. 18Mev) ~0

I00 2OO 3OO 4OO NO
TwnperaturL C
Fig. 31. Radiation-induced changes in electrical resistivity of
CSF graphite which was irradiated at temperatures between
300 and 1275C [45].
Fig. 33. Thermal conductivity of NC7 and NC8 graphites,
(Submitted by Pacific Northwest Laboratory, 1 November
1968).
graphites show little change in CTE before turnaround

the CTE of NC8 graphite and two raw coke graphites
decrease from 25 to 50% at fluences less than
TranswrN /
5 × 102] n/cm 2. The CTE of NC8 graphite increases
4
after turnaround in the same way as that of CSF
i graphite.
|
4.2.3. Thermal conductivity
15 The thermal conductivity of graphite is markedly
reduced by irradiation as shown in figs. 33 and 34. In
unirradiated graphite, the thermal conductivity
decreases as the temperature increases. For graphites
irradiated between 400 and 1000 C, the thermal con-
ductivity after irradiation is almost independent of
, I
4
, I
8
, 12
, I
16
, temperature. The thermal conductivity of a highly
crystalline graphite such as TSX is greater than that
Fast Neutron Fluenc~ I021Neutrons/era
2 (1[>(1 18Mevl
of a less crystalline graphite such as TSGBF after an
equivalent irradiation [50]. Irradiation at low tem-
Fig. 32. Radiation-induced changes in the mean coefficient of peratures reduces the thermal conductivity to a greater
thermal expansion of CSF graphite from 25 to 425 C for irra- extent than high-temperature irradiations. Irradiation
diation temperatures between 300 and 975 C [45]. at 30C to 1.0 × 1021 n/cm 2 reduces the thermal
0.4
l ~ o-- TSX
--.O---- C~
2.0
0.3 o-~ .L TSGBF
~o~ R
L6
1;
.--,
$
nl g
. , ~ • " -"
-
* II l'2xlOZllnvt-
l.OxI02 n~
| 1.2
-v " Irrillmtlon Tml~rature. C
/.~.~x.~ 9~-1275 C • 300-375 o 7B-~5

• 400-,475 a 9~-97p
0 , , , I i i J I i * ' I , , , I , i J I , ' ' I , , ,
f • ~0-.5~ a 1000-1075
I00 ZOO 300 400 ~0 6(]0 700
(111 o ~75Ja~ × llO0-lll5
Templrllturll, C 6,~0-7~0 v 1L~0-1275
I I I I i i
Fig. 34. Effect of irradiation at 650C on the thermal conduc- 4 8 12 16 20
tivity of graphite [50]. fest Nclutron fluence, IO 21 N e u t r o r l s / c m 2 (E > 0 . 1 8 M e v )
conductivity of CSF graphite to 0.005-0.007 cal/sec- Fig. 35. Effects of radiation and temperature on Young's mo-
cm-C. The thermal conductivity continues to decrease dulus of elasticity for CSF graphite (transverse) [45].
with increasing irradiation at 800 C for fluences up to
2.4 X 1022 n/cm 2. When graphite is irradiated in tension, some of the
imposed stress is relieved by irradiation creep. In the
4.3. Effects o f mechanical properties laboratory, the strain before fracture ranges from 0.1
Irradiation of graphite at low temperatures and to 0.2% for unirradiated graphite. When PGA graphite
low fluences produces a stronger and harder material. was irradiated at 300 to 420C to 1-2.2 × 1022
The compressive strength of KC graphite irradiated n/cm 2 , the creep strains ranged from 0.65 to greater
at 30C to 1.0 X 1021 n/cm 2 is about 2.5 times the than 2% [53]. Strains before fracture ranging from
initial unirradiated strength in the parallel direction 0.37 to 0.42% were measured in the parallel direction
[51 ]. Compressive and tensile strengths are reduced for NC8 graphite irradiated at 625 C at a nominal
at high fluences and high irradiation temperatures. strain rate of 0.13%/102° n/cm 2 [54]. Creep of
For example, the tensile strength of TSGBF graphite graphite in an irradiation environment provides a
at 25 C is reduced from 1560 psi before irradiation mechanism for relieving internal stresses which could
to 180 psi after irradiation at 1150C to 4.47 × 102] otherwise lead to fracture of graphite blocks, Com-
n/cm 2 , and the compressive strength at 25 C is reduc- pressive stresses of 150 and 300 psi increase the rate
ed from 8540 to 3410 psi [45]. Compressive of contraction of graphite irradiated at 625 C to
strength is also reduced by oxidation. The compres- 2 - 6 × 1020 n/cm 2 [55]. The compressive stress also
sive strength of PGA graphite at room temperature is reduces the initial expansion at fluences less than
reduced to 50% of the initial value by 14% oxida- 3 × 1020n/cm 2.
tion in-reactor [52]. Irradiation effects on mechani-
cal properties were removed by annealing at 1800 C 4.4. Stored energy
for one hour before compressive strengths were Radiation-induced damage to graphite, especially
measured. damage accumulated at temperatures less than 200 C,
Young's modulus of elasticity increases between increases the heat content of graphite. This increase
50 and 150% at low neutron fluences for conven- in heat content is called stored energy or Wigner
tional nuclear graphites such as CSF. As can be seen energy. When graphite, irradiated at low tempera-
in fig. 35, the largest changes occur at the lowest tures, is heated above the irradiation temperature,
irradiation temperatures and during the early stages some of the stored energy is released as heat. Heating
of the exposures. The changes in modulus for raw- of irradiated graphite can trigger a spontaneous
coke graphites are much larger. release of energy and under adiabatic conditions the
100 pore structure, particle size, temperature, pressure,

and other variables. Small amounts of impurities may
catalyze oxidation reactions. For example, 20 to 40
ppm of Na, K, V, or Cu increase the rate of oxida-
500
tion in air by a factor of 6 at 550C [2]. Oxidation is
400 uniform throughout a block of graphite at low tem-
peratures, but at elevated temperatures most of the
~0 attack occurs at the surface, and the rates are depen-
dent on the velocity of oxidant moving over the
surface. Chemisorption of the gaseous reactants on a
LO0
carbon surface is an essential step in the explanation
of gas-carbon reaction mechanisms [57].
I /
4
,
6
I J I
8
, Under normal reactor-temperature conditions,
Fast Neutron Fluence, 1020NeutronsJcmZ {E >0.18 Mev)
equilibrium considerations severely restrict the oc-
currence of some reactions, such as the production
Fig. 36. The accumulation of total stored energy in graphite of methane from hydrogen and carbon. Other reac-
at several irradiation temperatures [56]. tions, such as the formation of carbon monoxide
from carbon dioxide and graphite, are limited by
temperature may quickly rise several hundred degrees. kinetic considerations. By using thermochemical
The usual method of determining total stored energy data, particularly equilibrium constants, potential
consists of measuring the increase in the room-tem- chemical reactions leading to the gasification of
perature heat of combustion in an oxygen bomb graphite can be evaluated. Auxiliary reactions may
calorimeter. also occur between the gaseous reactants and reac-
The accumulation of stored energy as a function of tion products. In a nuclear reactor, graphite may
fluence is shown in fig. 36. When graphite is irra- interact with gases either in their molecular state or
diated to 5 X 1020 n/cm 2 at 30C, the total stored as highly reactive atomic species such as oxygen
energy is 630 cal/g. This amount of energy corres- atoms which normally exist only at very high tem-
ponds to the integrated heat capacity of unirradiated peratures.
graphite between 100 and 1550 C. The stored The heats of reaction of several gas-graphite sys-
energy of graphite irradiated at 30C approaches tems at 18 C and 1 atm pressure are given in table 11
saturation at 650 to 700 cal/g. As the irradiation tem- [58]. The standard free energy changes and equili-
perature increases, the saturation value of stored brium constants for a number of reactions in the
energy decreases and at moderator temperatures temperature range 300 to 2000 K are listed in
above about 350 C, stored energy assumes less impor- table 12 [59].
tance. The total stored energy in NC7 graphite
which expanded 19.8% from irradiation at 800 C to 5.2. Carbon dioxide-graphite system
a fluence of 2.4 X 1022 n/cm 2 was 115 cal/g. The The advantages of CO 2 for nuclear-reactor-
buildup of stored energy in graphite irradiated at coolant applications are universal availability, low
30 C is about 93 cal/g for each 0.1 A increase in c neutron-capture cross section, and low cost. At high
spacing. temperatures, however, the thermal reaction rates
with graphite are appreciable. The overall reaction is
C + CO 2 ~ 2CO. The equilibrium constants for this
5. Gas-graphite systems reaction are included in table 12. Fig. 37 shows the
equilibrium CO/CO 2 ratio in a CO 2 - graphite
5.1. Thermodynamics o f gas-graphite reactions system as a function of temperature [57]. At tem-
The reaction of graphite with oxidizing gases varies peratures above 625 C, oxidation occurs at a measur-
widely from one graphite grade to another. The reac- able rate, expressed by an equation of the form
tion rates depend on the crystal structure, impurities,
Table 11 oxidation rate with temperature is observed for the

Heats of reaction of several gas-graphite systems at 18 C and radiation-induced CO 2 graphite reaction at tempera-
1 atm pressure [58].
tures up to about 625 C. Above this temperature,
Reaction AH, kcal/mole
the thermal reaction becomes important. Over the
temperature range 30 to 300 C, the oxidation rate in-
(1) C + O2(g) = CO2(g) 94.03 creases only a factor of 2.
(2) C + ½02(g) = CO(g) -26.62 The effect of pressure on the radiation-induced
reaction rate is complex and depends on conditions
(3) CO(g) + ½02(g) = CO2(g) -67.41
of flow and geometry. In one study, a sevenfold
(4) C + CO2(g) = 2 CO(g) +40.79 increase in pressure increased the rate of reaction less
(5) C + H20(g) = CO(g) + H2(g) +31.14 than threefold [60].
(6) CO(g) + H20(g) = CO2(g) + H2(g) - 9.65
5.3. Oxygen-graphite system
(7) C + 2 H 2 = CH4(g) - 17.87
Air can be used directly as a coolant in contact
with graphite in nuclear reactors operating below
approximately 200 C [57]. At temperatures above
klPc02 about 400 C, thermal reactions of oxygen and graph-
Rate = - - ite overshadow the radiation-induced reactions. The
1 + k2Pc O + k3Pco 2 ' reaction of graphite with oxygen is represented by
eqs. 1 and 2 of table 11. Both CO 2 and CO are
where PCO and PCO2 are partial pressures of CO and primary products of the reaction. With increasing
LO2, and the constants are combinations of one or temperature, the ratio of CO to CO 2 in the products
more specific rate constants. The specific rate increases [58]. The graphite-oxygen reaction is
constants are exponential functions of the tempera- described by an equation of the form Rate = kp62 ,
ture. Each type of graphite will have different where k is an exponential function of the tempera-
constants. ture, PO is the oxygen partial pressure, and n is the
2
Carbon monoxide inhibits the reaction, as indi- reaction order. The reaction order found experimen-
cated by the term k2Pco in the rate expression. For tally is often close to t ; however, the order may vary
many carbons the constant k 2 decreases with increas- between 0 and 1, depending on the experimental
ing temperature. Thus, an increase in temperature conditions. Neither of the products of the graphite-
decreases the effectiveness of a given partial pressure oxygen reaction acts as an inhibitor.
of CO as an inhibitor. The equilibria represented by eqs. (1) and (2) of
In the temperature range 625 to 950 C, the reac- table 11 are displaced far toward the product side,
tion rate is controlled by the chemical reactivity of so that the presence of an excess of CO 2 or CO has a
the solid, and the activation energy is approximately negligible effect on the reaction rate. The rates of
93 kcal/mole [57]. From 950 to 1250 C, oxidation reaction of CSF graphite with oxygen and air as
rates are controlled by diffusion of reactants and pro- functions of temperature are shown in fig. 39. At
ducts through the solid, and the apparent activation 450 C, the oxidation rate is proportional to the 0.45
energy, roughly 46 kcal/mote, is about one half that power of the oxygen partial pressure, and at 675 C
at lower temperatures. The temperature dependence the exponent is 0.93. A value of 0.5 is probably a
of the reaction of graphite with CO 2 at 1 atm is reasonable approximation for the order of the
shown in fig. 38. reaction. A wide range of activation energies for oxi-
When CO 2 is irradiated in the presence of graphite, dation of graphite has been reported, and it now
CO is produced until steady-state conditions are appears that the correct value for very pure graphite
reached. The effects of variables such as temperature, lies between 60 and 65 kcal/mole [62]. Less pure
pressure, flow rate, and radiation intensity on the graphites have lower values (around 40 kcal/mole).
kinetics of the radiation-induced CO 2 graphite reac- The data given in fig. 39 for CSF graphite may be
tion have been studied [60]. Very little change in extrapolated to other temperatures and oxygen
Table 12
Standard free energy changes a and equilibrium constants b for several gas-graphite reactions [591.
C + 0 2 =CO2 C + ~O2 = CO C + O =CO C + H 2 0 = C O + H2 C + 2 H 2 0 = CO2 + 2H2 CO + ]-]2° = CO2 + H2

Temp.
1 O0 K ~tF o log Kp AF° log Kp AF° log Kp AF° log Kp AF° log Kp AF° log Kp
3 -94.248 68.656 -32.821 23.909 -88.191 64.243 21.795 -15.877 14.984 -10.915 - 6.811 4.962
4 -94.314 51.528 -34.973 19.107 -88.921 48.581 18.544 -10.131 12.720 - 6.950 - 5.824 3.182
5 -94.376 41.250 -37.141 16.234 -89.627 39.174 15.218 - 6.651 10.342 - 4.520 - 4.876 2.131
6 -94.434 34.396 -39.309 14.318 -90.306 32.892 11.846 - 4.315 7.876 - 2.869 - 3.970 1.446
7 -94.484 29.498 -41.466 12.946 -90.954 28.395 8.446 - 2.637 5.340 - 1.667 - 3.106 0.970
8 -94.526 25.822 -43.609 11.913 -91.572 25.015 5.034 - 1.375 2.760 - 0.754 - 2.274 0.621
9 -94.563 22.962 -45.739 11.106 -92.164 22.379 1.610 - 0.391 0.135 - 0.033 - 1.475 0.358
10 -94.594 20.673 -47.856 10.458 -92.733 20.266 - 1.819 0.398 - 2.520 0.551 - 0.701 0.153
11 -94.617 18.798 -49.956 9.925 -93.278 18.532 - 5.248 1.043 - 5.201 1.033 0.047 -0.009
12 -94.638 17.235 -52.046 9.478 -93.805 17.083 - 8.679 1.581 - 7.904 1.439 0.775 -0.141
13 -94.653 15.912 -54.121 9.098 -94.310 15.854 -12.104 2.035 -10.619 1.785 1.485 -0.250
14 -94.663 14.777 -56.185 8.770 -94.801 14.798 -15.528 2.424 -13.349 2.084 2.179 -0.340
t~
15 -94.672 13.793 -58.238 8.485 -95.274 13.881 -18.946 2.760 -16.088 2.344 2.858 -0.416
16 -94.676 12.932 -60.280 8.234 -95.733 13.076 -22.358 3.054 -18.832 2.572 3.526 -0.482
17 -94.676 12.171 -62.311 8.010 -96.177 12.364 -25.767 3.312 -21.588 2.775 4.179 -0.537
18 -94.671 11.494 -64.332 7.811 -96.608 11.729 -29.167 3.541 -24.341 2.955 4.826 -0.586
19 -94.665 10.888 -66.344 7.631 -97.028 11.160 -32.564 3.746 -27.105 3.118 5.459 -0.628
20 -94.655 10.343 -68.348 7.468 -97.437 10.647 -35.955 3.929 -29.869 3.264 6.086 -0.665
CO + O = CO2 C+O3=CO+O2 C + C O 2 = 2CO 4CO = CO2 + C 3 0 2 C+OH=CO+H C + 2H2 = CH4
3 -116.797 85.080 - 71.761 52.275 28.606 -20.838 26.295 -19.155 7.557 - 5.505 -12.106 8.819
4 -113.289 61.895 - 75.574 41.290 24.368 -13.313 33.987 -18.569 4.585 - 2.505 -10.063 5.498 c~
5 -109.721 47.956 - 79.413 34.710 20.094 - 8.783 41.694 -18.224 1.560 - 0.682 - 7.840 3.427
6 -106.122 38.651 - 83.249 30.322 15.816 - 5.761 49.378 -17.985 - 1.498 0.546 - 5.488 1.999
7 -102.506 32.001 - 87.071 27.183 11.552 - 3.606 57.018 -17.801 - 4.575 1.428 - 3.041 0.949
8 - 98.880 27.011 - 90.871 24.824 7.308 - 1.996 64.611 -17.650 - 7.663 2.093 0.526 0.144
9 - 95.249 23.128 - 94.650 22.983 3.085 - 0.749 72.155 -17.521 -10.761 2.613 2.038 -0.495
10 - 91.615 20.021 - 98.411 21.507 - 1.118 0.244 79.654 -17.408 -13.867 3.030 4.634 -1.013
11 - 87.983 17.480 -102.152 20.294 - 5.295 1.052 87.105 -17.305 -16.975 3.372 7.257 -1.442
12 - 84.351 15.362 -105.875 19.281 - 9.454 1.722 94.518 -17.213 -20.087 3.658 9.897 -1.802
13 - 80.721 13.570 -109.580 18.421 -13.589 2.284 101.884 -17.127 -23.199 3.900 12.547 -2.109
14 - 77.094 12.034 -113.271 17.681 -17.707 2.764 109.218 -17.048 -26.313 4.107 15.206 -2.374
15 - 73.470 10.704 -116.946 17.03~ -21.804 3.177 116.511 -16.974 -29.426 4.287 17.871 -2.604
16 - 69.849 9.540 -120.609 16.473 -25.884 3.535 123.769 -16.905 -32.538 4.444 20.533 -2.805
17 - 66.231 8.514 -124.257 15.973 -29.946 3.850 130.997 -16.839 -35.648 4.583 23.204 -2.983
18 - 62.615 7.602 -127.895 15.527 -33.993 4.127 138.196 -16.778 -38.755 4.705 25.871 -3.141
19 - 59.005 6.787 -131.524 15.127 -38.023 4.373 145.360 -16.719 -41.862 4.815 28.538 -3.282
,.--.I
20 - 55.396 6.053 -135.143 14.767 -42.041 4.594 152.500 -16.663 -44.968 4.914 31.203 -3.410
-AF ° AF °
a. Units o f AF ° are kcal/mole, b. Given as logl0 Kp, which equals ~ , or - 2 1 8 . 5 4
T,K
100
. %\
,%
10"1 -- \\\
lO
Total Pressure. aim %\\\\
10 -2
T'
LO
.!
] 10"3 Rele in Air
rll
10 -4
O.Ol I I
I , I , I 1
800 ~0 log0 ll00 I/W ~ 1400
Tmllrllure. K 10"5 I , I I I ,
1.1o 1.20 1.~
Fig. 37. Equilibrium CO/CO2 ratio in a CO2-graphite system IO001T,K
with no CO present initially [57]. l , I , l , l ,
600 550
Temperature, C
Fig. 39. CSF graphite oxidation data [16].

lO0
partial pressures by means o f the equation
%
%% Rate (hr - 1 ) = 5.56 X 1010
× exp(-49.86 X IO3/RT) (po2)0.5,
where PO2 is in atmospheric units, T is in degrees Kel-

vin a n d R is the gas constant in cal/mole degree.
o, ",.~ %% These data apply to small graphite samples in which
t the entire volume is oxidized homogeneously. At oxi-
dation rates greater than about 10 -4 hr -1 in
0.1
10 × 10 cm cross section blocks, the rapid reaction is
limited to the outer surface and prevents oxygen
from diffusing to the interior of the block.
0.01 N,
IN aE 5.4. S t e a m - g r a p h i t e s y s t e m
O.W
The thermal reactions o f graphite with steam and
ll~fl', K
graphite with carbon dioxide are similar in mechan-
ism and in the rate o f reaction. The reaction products
are carbon monoxide, carbon dioxide, hydrogen, and
methane. The primary reactions are probably
Fig. 38. Temperature dependence of the rate of reaction of
spectroscopic carbon rods with CO2 at 1 atm [58]. The car- C + H 2 0 ~ CO + H 2
bon rods were manufactured from lamp-black and heat-
treated at 3000C. C+2H20~CO 2 +2H 2.
Secondary reactions are

10";~
C + 2H 2 ~ CH 4
10-3 -
C + CO 2 ~ 2 CO. 900C
The rate equation is of the form

IO00C
10.4
klPH20
Rate - 800C
1 + k 2 P n 2 -4- k3Pn20 '
~: 10.5
where PH20 and PH2 are the partial pressures of water
vapor and hydrogen, respectively. The temperature
and pressure dependence of the reaction rate is deter- 10.4
mined by the relative magnitudes of the terms in the

denominator of the rate equation. The reaction order
10"/
with respect to water vapor can vary from zero to one
depending upon the conditions of the reaction. Thus,
in fig. 40, at 600 C the reaction is zero order with 10-8
respect to water vapor, whereas, at 1000 C it is essen- ~C
tially first order. Hydrogen acts as an inhibitor of the I , I , I I
10.9
steam-graphite reaction, but with increasing tempera- 10"1 10.2 10"] 104
tures the constant k 2 decreases and, thus, the effec- Partial Pressure d WI~" Vl~r 1~/~, aim
tiveness of hydrogen as an inhibitor also decreases. At

steam pressures of 0.1 to 10 torr and hydrogen Fig. 40. The thermal reaction of graphite with water vapor
pressures from 0.08 to 8.0 torr, ( p H 2 ) l w a s used in [63].
place ofPH 2 in the rate equation to fit the low-
pressure oxidation data [64]. Carbon monoxide is not The activation energy for methane production
an effective inhibitor of the steam-graphite reaction, from carbon and hydrogen is in the range of 65 to 70
but it does compete with graphite for water vapor kcal/mole at temperatures above 515 to 600 C and
by the water-gas shift reaction 10 to 12 kcal/mole at lower temperatures [67,68].
The back reaction, the thermal decomposition of
C O + H 2 0 =CO 2 + H 2.
methane, is first order with respect to the methane
concentration.
5.5. H y d r o g e n - graphite s y s t e m Radiation has a pronounced effect on the reaction
The reaction of hydrogen and graphite produces of graphite with hydrogen by forming highly reactive
methane as the principal product between 350 and species in the gas phase [57]. The active species are
1700 C. The equation for the overall reaction is believed to be hydrogen atoms or ionized hydrogen
molecules with very short lifetimes. When the
C + 2H 2 ~ CH 4 .
hydrogen-graphite system is exposed to radiation
As the temperature is increased, the production of within a reactor, methane is formed at temperatures
methane from the forward reaction is decreased. At at- where the thermal reaction is extremely slow. The
mospheric pressure and temperatures above 1000C, rate of methane production is approximately propor-
less than 1% CH 4 is present at equilibrium as shown in tional to the hydrogen pressure in the range 400 to
fig. 41. Above 1700C acetylene is formed by the 800 torr. The activation energy for the radiation-in-
reaction duced reaction is probably less than 10 kcal/mole.
The G value (the number of molecules formed per
2C + H 2 ~ C2H 2 .
100 eV absorbed by the hydrogen) depends upon
The equilibrium yield of acetylene increases with the volume of hydrogen used in the calculation. Con-
temperature up to 3200 C [65,66]. sideration of only the hydrogen within the pores of
the graphite results in an average G value of about 10.
of the metal halides [72]. The coating temperature and

pressure are chosen to prevent metal deposition, but
LO to allow the formation of the carbide.
O.8
6. Compatibility with metals and ceramics
c 6.1. Reactions with metals

Most metals react with graphite at high tempera-
0.4
tures to form carbides. The compatibility of metals
3O 1~
and ceramics in contact with graphite cannot be pre-
dicted with accuracy because the extent of reaction
11,2
depends upon physical factors as well as thermo-
dynamic properties. Finely dispersed powders react
more rapidly than massive bodies at a given tempera-
ture. Most carbides are stable although some hydro-
T~llt ure. C
lyze is moist air. The temperatures and products of
Fig. 41. The mole fraction of methane formed at equilibrium several metal-graphite reactions are given in table 13.
for the hydrogen-graphite reaction [57 ]. In some cases the temperatures listed in the table
are the result of observations of reactions for short
5.6. lnhibitors and protective coatings time intervals such as a few hours; however, the reac-
Inhibitors of protective coatings may be used to re- tions may also proceed with reduced rates at lower
duce graphite oxidation at high temperatures. Com- temperatures. The conditions for the reaction of a
pounds containing phosphorus, such as trimethyl metal and graphite are often not well defined, which
phosphate, phosphorus pentoxide and phosphoric accounts for some of the contradictory results.
acid, inhibit graphite oxidation in the absence of radia- In the liquid-metal-fueled reactor concept, unclad
tion, but they are ineffective in nuclear reactors [57]. graphite is used as the moderator and container for
Certain halogen compounds are effective gas phase the bismuth coolant. The absorption of liquid
oxidation inhibitors. Two percent chlorine in an bismuth by graphite is a function of the surface ten-
oxygen stream will extinguish burning in petroleum sion of bismuth, pressure, and time [73]. The up-
coke at 1730 C and in nuclear graphite at 1200 C take of bismuth at 550C and 250 psi for a low
[69]. permeability graphite such as H4LM is about
One of the most successful carbide coatings for 0.5 g/cm 3 of graphite. The surfaces of graphite
graphite is silicon carbide. The base graphite must be which were submerged in bismuth for 104 hr
isotropic and have a thermal expansion coefficient showed no evidence of erosion, spalling or surface
close to that of silicon carbide. Silicon carbide fractures [74].
coatings provide protection to graphite for a few Graphite reacts with the alkali metals to form
hundred hours in 1000 C air without failure [70]. lamellar compounds. Unirradiated graphite expands
Silicon carbide-coated graphites were irradiated at about 1% when it is exposed to liquid sodium at
600 C to 8 X 1020 n/cm 2 and subsequently heated for 200 and 500 C. The amount of expansion does not
575 hr at 1000 C in air without failure. Irradiated appear to be temperature dependent. Some cracking
samples were also thermally cycled between 250 and occurs in materials which are graphitized at low
1200 C for 1000 cycles without generating cracks in temperatures or contain nongraphitic carbon. The
the SiC coating [71 ]. The best silicon carbide lamellar compound C64Na was identified by X-ray
coatings were 0.005 to 0.010 in. thick and had no diffraction analysis and is believed to have a structure
sharp corners. Other coating systems include the car- in which the sodium is intercalated in every eighth
bides of niobium, tantalum, and zirconium which are layer plane [75]. Sodium can be removed from
formed on graphite by the thermal decomposition graphite almost quantitatively by vacuum distillation.
Table 13 Table 14
Reactions with metals [8]. Temperatures for metal oxide-graphite reaction [8,80-82].
Metal Temperature, C Product or effect Oxide Temperature, C

AI 800 A14C3 ; reaction rapid at 1400 C A1203 1350
B 1600 B4C; commercially prepared at B203 1200
2400C BeO > 1400
Be 900 Be2C in vacuum or helium CaO 1305
Bi 550 No attack in 104 hr for low per- CeO2 800
meability graphite Cr203 690
Co 218 CoaC, metastable HfO2 1700
Cs CsCs and other intermediate La203 700
lamellar compounds to MgO 950-1000
C6oCs at vapor pressures PuO2 850
> 10-4 torr
SiO2 1250
Cu 1010 No attack in 250 hr Ta20 s 1100
Fe 600-800 FeaC ThO2 1380
Hf 2000 HfC TiO2 1100
K 65 CsK and other lamellax UO2 800
compounds V20s 650
Li 500 Li2C2 Zr02 900-1000
Mg 650 No attack near melting point
Mo 700 Mo2C; MoC > 1200C
Na I00 C64Na lameUarcompound
Nb 700 NbC and Nb2C; layer diffuses exposed to sodium at 150 C, small cracks and about
0.003 in. at 1010 C in 1% expansion occur, whereas graphite irradiated at
2000 hr
50 C to 102o n/cm 2 disintegrates to a granular mass
Ni 1310 No stable carbides; solubility
of C in Ni at the eutectic under similar conditions. Anisotropic behavior in ex-
temperature (1316C) is pansion is observed with greater expansion occur-
0.65 w/o ring transverse to the axis of extrusion.
Pb 1090 No attack after 24 hr by Pb in
Pb-Bi eutectic
6.2. Reactions with metal alloys and molten salts
Pu 1050 PuC in vacuum; Pu2C 3 with
excess carbon; The c o m m o n heat resistant nickel-base and iron-
PuC2 > 1750C base alloys contain a high percentage of carbide form-
Rb CaRb and other lameUar com- ing elements. Carburization of numerous alloys is
pounds at temperatures observed in helium when the alloys are heated in
where vapor pressure is a
few torr contact with graphite at temperatures ranging from
Si 1150 #-SIC 700 to 1000 C and at applied loads of 2000 psi [77].
Sn 850-1000 No corrosion after 60 hr Nickel-base alloys and stainless steels carburize
Ta 1400 Ta2C and TaC; 5 X 10-4 in. rapidly above 816 C. The Fe-Cr-A1 alloy, DB-2,
carbide layer in 24 hr at resists carburization at 704 and 816 C in 2000 hr
1400C
Th 2100 ThC; ThC2 in vacuum tests but at 927 C carburization is complete. The
Zr 750 ZrC alloys Inconel, Inconel 702 and Nichrome V carburize
rapidly at 704 C. The austenitic steel alloys exhibit
relatively low resistance to carburization due to the
Graphite irradiated in the 102°-1021 n/cm 2 range at high solubility of carbon in austenite. Type 304
300 to 500C expands 2 to 5% when heated at 425 to stainless steel is particularly susceptible to carburiza-
650 C with sodium [76]. The sodium - induced ex- tion whereas stainless steels with higher chromium
pansion of irradiated graphite depends on the radia- content are somewhat more carburization resistant
tion temperature and neutron fluence. When graphite up to 816C.
is irradiated at 600C to 1021 n/cm 2 and subsequently Graphite does not react chemically with the LiF-
442 D.L: Baker. Graphite as a neutron moderator and reflector material
BeF2-UF 4 molten salt system which is used in the [7] R.G.Donnelly and G.M.Slaughter, The Brazing of
MSRE. The penetration of molten salt into graphite is Graphite, Welding J. 41 (1962) 461-469.
a function of the applied pressure, surface tension of [8] R.E.Nightingale (Ed.), Nuclear Graphite, Chapter 6
the nonwetting molten salt, and the pore size distribu- Physical Properties (Academic Press Inc., New York,
1962) pp. 117 194.
tion of the graphite [78,83]. The absorption of
[9] J.Glasser and W.J.Glasser, Directory of Graphite Avail-
molten salt at 700 C was measured for more than 15 ability, Second Edition, Report AFML-TR-67-113,
different graphites [79]. Less than 0.5% of the bulk Chemical and Metallurgical Research, Inc., August
volume of the graphite was permeated by the salt for 1967.
some specimens. One hundred cycles between 200 [ 10] R.E.Nightingale (Ed.), Nuclear Graphite, Chapter 5 -
and 700 C produced no detectable change in proper- Structure (Academic Press Inc., New York, 1962)
pp. 87-115.
ties or appearance.
[ 11 ] J.B.Nelson and D.P.Riley, The Thermal Expansion of
Graphite From 15C to 800C. Part I. Experimental,
6.3. R e a c t i o n s w i t h c e r a m i c s Proc. Phys. Soc., London 57 (1945) 477-486.
Many ceramic oxides are reduced by graphite to [12] R.E.Nightingale (Ed.), Nuclear Graphite, Chapter 4 -
Nuclear Properties (Academic Press Inc., New York,
the metals or, with an excess of graphite, to the
1962) pp. 67-85.
carbides. The equilibrium for the reaction of a metal [13] K.S.Pitzer and E.Clementi, Large Molecules in Carbon
oxide, MexOy, with carbon Vapor, J. Am. Chem. Soc. 81 (1959) 4477-4485.
MexOy + yC = yCO + xMe is shifted to the right [14] G.J.Schoessow, Graphite Triple Point and Solidus-
by both high vacuum and high temperature. A Liquidus Interface Experimentally Determined Up to
general reaction for the formation of the carbide is 1000 Atmospheres, Report NASA CR-1148, University
of Florida, July 1968.
given by [15] W.Desorbo and W.W.Taylor,The Specific Heat of
Graphite from 13 to 300K, J. Chem. Phys. 21 (1953)
2MexOy + 3yC = 2yCO + Me2xCy . 1660-1663.
The formation of solid phases at the reaction interface [16] F.D.Rossini, K.S.Pitzer, R.L.Arnett, R.M.Braun and
may reduce the reaction rate by mechanically separat- G.C.Pimentel, Selected Values of Physical and Thermo-
dynamic Properties of Hydrocarbons and Related
ing the reactants or by acting as diffusion barriers. Compounds Comprising the Tables of the American
The temperatures of reaction of several metal oxides Petroleum Institute Research Project 44 (Carnegie
with graphite are given in table 14. Press, Pittsburgh, 1953).
[ 17] H.M.Spencer, Empirical Heat Capacity Equations of
Gases and Graphite, Ind. Eng. Chem. 40 (1948)
2152-2154.
References [18] G.B.Spence, Survey and Analytical Representation of
the Measurements of the Specific Heat of Graphite, Re-
I 1] R.E.Nightingale.(Ed.), Nuclear Graphite, Chapter 2 -
port WADD TR 61-72 Vol. XLI, Air Force Materials
Manufacture (Academic Press Inc., New York, 1962) Laboratory, November 1962.
pp. 22-51. [ 19] R.Taylor, The Thermal Conductivity of Pyrolytic
[2] L.M.Curie, V.C.Hamister and H.G.MacPherson, The Pro- Graphite, Phil. Mag. 13 (1966) 157-166.
duction and Properties of Graphite for Reactors, in: [20] The Industrial Graphite Engineering Handbook (Union
Proceedings of the International Conference on the Carbide Corp., New York, 1959).
Peaceful Uses of Atomic Energy held in Geneva, August [21] P.Wagnerand L.B.Dauelsberg, The Thermal Conduc-
1955, United Nations, New York, 1956. tivity of ZTA Graphite, Carbon 5 (1967) 271-279.
[3] R.J.Diefendorf and E.R.Stover, Pyrolytic Graphites - [22] Research and Development on Advanced Graphite
How Structure Affects Properties, Metal Progress 81 Materials, Report WADD Technical Note 61-18, U.S.
(1962) 103-108. Air Force, April 1961.
[4] R.E.Nightingale (Ed.), Nuclear Graphite, Chapter 3 -
[23] R.M.Bushong and E.A.Neel, Properties of High Densi-
Machining Practice (Academic Press Inc., New York, ty Recrystallized Graphite, in Proceedings of the
1962) pp. 53-65.
Fifth Conference on Carbon held in University Park,
[5] C.R.Tipton Jr. (Ed.), Reactor Handbook, Vol. 1 - Pennsylvania, Vol. 1 (The MacMillanCompany, New
Materials, 2nd ed. (Interscience, New York, 1960) York, 1963) pp. 595-599.
pp. 888-896.
[24] J.D.Plunkett and W.D.Kingery,The Spectral and Inte-
[6] B.J.Goulding, Clean Conditions during Graphite grated Emissivity of Carbon and Graphite, in Proceed-
Machining and Storage, Nucl. Eng. 7 (1962) 29-30. ings of the Fourth Conference on Carbon held in
Buffalo, New York (Pergamon Press, New York, [39] G.R.Tully Jr. and B.F.Disselhorst, A Process for Making
1960) pp. 457-472. Graphites Less Permeable to Gases at High Tempera-
[25] l.E.CampbeU (Ed.), High Temperature Technology, tures, USAEC Report GA-2318, General Atomic
Chapter 4 - Properties of Carbon and Graphite at Division, General Dynamics Corp., February 1963.
High Temperatures (Wiley, New York, 1960) [40] D.A.Boyland, The Reduction of the Permeability of
pp. 92-111. Graphite, G.E.C. Atomic Energy Rev. 2 (1959)
[ 26 ] Pyrolytic Graphite Engineering Handbook (General 44-50.
Electric Co., Detroit, 1963). [41] J.H.Cox Jr., Pacific Northwest Laboratory, personal
[27] R.G.Merryman, P.Wagner and D.P.MacMillan, H4LM communication, October 1967.
Graphite, USAEC Report LAMS-2725, Los Alamos [42] J.W.Helm and J.M.Davidson, Effect of Massive Neutron
Scientific Laboratory, September 1962. Exposure on the Distortion of Reactor Graphite, Carbon
[28] M.C.Smith, D.J.Eash and K.McKibbin, Longitudinal 1 (1964) 435-439.
Tensile Properties of H4LM Graphite in the Tempera- [43] H.H.Yoshikawa, E.M.Woodruff, J.M.Davidson, J.W.
ture Range - 253 to 500C, Carbon 1 (1964) Helm and R.E.Nightingale, Radiation Effects in
181-183. Carbons and Graphites, in: Radiation Damage in Reac-
[29] G.W.Rowe, High Temperature Strength of Clean tor Materials (International Atomic Energy Agency,
Graphite, Nucl. Eng. 7 (1963) 102-103. Vienna, 1963) pp. 581-592.
[30] R.J.Diefendorf, The Effect of Atmosphere on the [44] J.W.Helm, Long-Term Radiation Effects on Graphite,
Strength of Graphite, in: Proceedings of the Fourth for the Eighth Biennial Conference on Carbon held in
Conference on Carbon held in Buffalo, New York Buffalo, New York, June 1967, USAEC Report BNWL-
(Pergamon Press, New York, 1960) pp. 489-496. SA-1108, May 1967.
[31] W.V.Kotlensky and H.E.Martens, Mechanical Proper- [45] J,H.Cox and J.W.Helm, Graphite Irradiations 300 ° -
ties of Pyrolytic Graphite to 2800 C, in Proceedings 1200°C, Carbon 7 (1969) 319-327.
of the Fifth Conference on Carbon held in University [46] G.B.Engle, Dimensional and Property Changes of Im-
Park, Pennsylvania, Vol. 2 (The MacMillan Company, pregnated and Isotropic Graphites Irradiated at 300 to
New York, 1963) pp. 625-638. 1500 C, USAEC Report GA-7326, General Atomic
[32] C.Rounthwaite, G.A.Lyons and R.A.Snowdon, In- Division, General Dynamics Corp., April 1967.
fluence of Thermal Corrosion on the Strength, Per- [47] J.W.Helm, Pacific Northwest Laboratory, personal com-
meability and Frictional Properties of Nuclear Graphite, munication, November 1967.
in Second Conference on Industrial Carbon and [48] F.W.Albaugh, S.H.Bush, J.J.Cadwell, D.R.deHalas and
Graphite held in London, April 1965 (Society of D.C.Worlton, Quarterly Progress report April, May,
Chemical Industry, London, 1966) pp. 299-319. June 1967, Reactor Fuels and Materials Development
[33] P.Wagner, A.R.Driesner and E.A.Kmetko, Some Mecha- Programs for Fuels and Materials Branch of USAEC
nical Properties of Graphite in the Temperature Range Division of Reactor Development and Technology,
20 to 3000 C, in: Proceedings of the Second United USAEC Report, BNWL-473, Pacific Northwest Labora-
Nations International Conference on the Peaceful tory, September 1967.
Uses of Atomic Energy, Vol. 7 - Reactor Technology [49] R.E.Nightingale and E.M.Woodruff, Radiation-lnduced
(United Nations, Geneva, 1958) pp. 379-388. Dimensional Changes in Large Graphite Bars, Nucl. Sci.
[34] A.C.Collins, H.G.Masterson and P.P.Jennings, The Eng. 19 (1964) 390-392.
Effect of Oxidation on the Compressive Strength of [50] D.E.Baker, Thermal Conductivity of Irradiated Graphite
Graphite, J. Nucl. Mater. 15 (1965) 135-136. by a Rapid Thermal-Pulse Method, J. Nucl. Mater. 12
[35] P.E.Armstrong and H.L.Brown, Dynamic Young's Modu- (1964) 120-124.
lus Measurements above 1000C on Some Pure Poly- [51] W.K.Woods, L.P.Bupp and J.F.Fletcher, Irradiation
crystalline Metals and Commercial Graphites, Trans. Damage to Artificial Graphite, in: Proceedings of the
Met. Soc. AIME 230 (1964) 962-966. International Conference on the Peaceful Uses of
[36] W.P.Eatherly, MJanes, R.L.Mansfield, R.A.Bourdeau Atomic Energy, Geneva, 1955, Vol. 7 (United Nations
and R.A.Meyer, Physical Properties of Graphite Mater- New York, 1956) pp. 455-471.
ials for Special Nuclear Applications, in: Proceedings of [52] N.Hawkins, Effect of Radiolytic Corrosion on the
the Second United Nations International Conference on Mechanical Properties of Graphite, in: Second Confer-
the Peaceful Uses of Atomic Energy, Vol. 7 - Reactor ence on Industrial Carbon and Graphite held in
Technology (United Nations, Geneva, 1958) pp. 379- London, April 1965 (Society of Chemical Industry,
388. London, 1966) pp. 355-366.
[37] C.C.Horton and L.E.J.Roberts, The Adsorption of Water [53] A.J.Perks and J.H.W.Simmons, Dimensional Changes
on Pile Graphite, British Report AERE-C-R-2219, and Radiation Creep of Graphite at Very High Neu-
1958. tron Doses, Carbon 4 (1966) 35-98.
[38] L.G.Overholster and J.P.Blakely, Outgassing Character- [54] J.L.Jackson, The Tensile Fracture Strain of Graphite
istics of Various Graphites, USAEC Report ORNL- Determined During Neutron Irradiation~ Carbon 3
3396, Oak Ridge National Laboratory, March 1963. (1966) 397-400.
[551 W.C.Morgan, Effect of Low Compressive Stresses on [70] J.L.Jackson, The Effect of Irradiation on Siliconized
Radiation-Induced Dimensional Changes in Graphite, Silicon Carbide Coatings for Graphite, USAEC Report
Carbon 1 (1964) 255-261. HW-68494, Hanford Atomic Products Operation,
[ 56 ] R.E.Nightingale (Ed.), Nuclear Graphite, Chapter 12 - General Electric Company, February 1961.
Stored Energy (Academic Press Inc., New York, 1962) [71 ] J.L.J ackson, The Effect of Oxidation, Thermal Cycling,
pp. 325-353. and Irradiation on Silicon Carbide (SIC) Coated
[57] R.E.Nightingale (Ed.), Nuclear Graphite, Chapter 14 - Graphite, USAEC Report BNWL-242, Pacific North-
Gas-Graphite Systems (Academic Press Inc., New York, west Laboratory, August 1966.
1962) pp. 387-444. [72] J.M.Blocher, C.J.Ish, D.P.Leiter, L.F.Plock and I.E.
[58] P.L.Walker Jr., F.Rusinko Jr. and L.G.Austin, Gas Campbell, Carbide Coatings on Graphite, USAEC
Reactions of Carbon, in Advances in Catalysis and Re- Report BMI-1200, Battelle Memorial Institute, June
lated Subjects, Vol. XI (Academic Press Inc., New 1957.
York, 1959) pp. 133-221. [731 R.E.Nightingale (Ed.), Nuclear Graphite, Chapter 15 -
[59] R.E.Woodley, Standard Free Energy Changes and Graphite - Metal and Graphite - Molten Salt Systems,
Equilibrium Constants for Gas-Graphite Reactions in (Academic Press Inc., New York, 1962) pp. 445-463.
the Temperature Range 300-2000 K, USAEC Report [74] C.J.Klamut, D.G.Schweitzer, J.G.Y.Chow, R.A.Meyer,
HW-73523, Hanford Laboratories, General Electric O.F.Kammerer, J.R.Weeks and D.H.Gurinsky, Material
Company, May 1962. and Fuel Technology for an LMFR, in: Proceedings of
[60] P.C.Davidge and W.R.Marsh, The Effect of Pile Radia- the Second United Nations International Conference
tion on the Carbon Dioxide-Graphite Reaction, on the Peaceful Uses of Atomic Energy, Vol. 7 - Reac-
British Report AERE-C/R-1374, 1955. tor Technology (United Nations, Geneva, 1958)
[61] R.E.Dahl, Oxidation of Graphite under High Tempera- pp. 173-195.
ture Reactor Conditions, USAEC Report HW-68493, [75] R.C.Asher and S.A.Wilson, LameUar Compound of
Hanford Laboratories, General Electric Company, Sodium with Graphite, Nature 181 (1958) 409-410.
July 1961. [76] D.L.Henry, K.T.MiUer and J.D.Stearns, The Effect of
[62] J.B.Lewis, The Thermal Reactivity of Nuclear Grade Neutron Irradiation on the Liquid Sodium Dilation of
Graphites to Oxygen, in Progress in Nuclear Energy, Graphite, USAEC Report NAA-SR-11309, Atomics
Ser. IV, Vol. 5 (MacMillan, New York, 1963) pp. 145- International, June 1965.
171. [ 77 ] J.C.Bokros, Graphite-Metal Compatibility at Elevated
[63] R.E.Woodley, A Review of the Reactions of Nuclear Temperatures, J. Nucl. Mater. 3 (1961) 89-100.
Graphite with Oxygen and Water Vapor, USAEC [78] Molten-Salt Reactor Program, Semiannual Progress
Report HW-75072, Hanford Atomic Products Opera- Report for Period Ending July 31, 1964, USAEC
tion, General Electric Company, September 1962. Report ORNL-3708, Oak Ridge National Laboratory,
[64] R.C.Giberson and J.P.Walker, Reaction of Nuclear November 1964.
Graphite with Water Vapor, Part I Effect of Hydrogen [79] Molten-Salt Reactor Program, Quarterly Progess Report
and Water Vapor Partial Pressures, Carbon 3 (1966) for Period Ending October 31, 1959, USAEC Report
521-525. ORNL-2890, Oak Ridge National Laboratory, March
[65] J.T.Clarke and B.R.Fox, Reaction of Graphite Fila- 1960.
ments with Hydrogen above 2000 K, J. Chem. Phys. [80] W.J.Kroll and A.W.Schlechton, Reactions of Carbon
46 (1967) 827-836. and Metal Oxides in a Vacuum, J. Electrochem. Soc.
[66] R.F.Baddour and J.M.lwasyk, Reactions between Ele- 93 (1948) 247-258.
mental Carbon and Hydrogen at Temperatures above [81] W.H.Pfeifer, G.W.Cunningham, D.C.Carmichael and
2800K, IEC Proc. Des. Dev. 1 (1962) 169-176. E.S.Hodge, Resistance of Ceramic Fuel-Particle Coatings
[67] P.Breisacher and P.C.Marx, The Hydrogen - Graphite to Reactions with Oxygen and Graphite, USAEC
Reactions between 360 and 800C, J. Am. Chem. Soc. Report BMI-1647, Battelle Memorial Institute, Septem-
85 (1963) 3518-3519. ber 1963.
[68] N.S.Corney and R.B.Thomas, The Effect of Pile Radia- [82] D.A.Schulz, P.H.Higgs and J.D.Cannon, Research and
tion on the Reaction between Hydrogen and Graphite, Development on Advanced Graphite Materials, Vol. 34,
British Report AERE-C/R-2502, June 1958. Oxidation Resistant Coatings for Graphite, Report
[69] R.E.Dahl, Evaluation of Chlorine Inhibition of Graphite WADD TR 61-72 Vol. 34 (Union Carbide Corporation,
Oxidation as a Reactor Safeguard, USAEC Report July 1964).
HW-67255, Hanford Atomic Products Operation, [83] P.R.Kasten et al., Graphite behavior and its effect on
General Electric Company, April 1961. MSBR Performance, Nucl. Eng. Design 9 (1969)
157-195.

Baker 1971

Uploaded by

Copyright:

Available Formats

Baker 1971

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Baker 1971

Uploaded by

Copyright:

Available Formats

NUCLEAR ENGINEERINGAND DESIGN 14 (1970) 413-444.

1. Introduction aceous materials, rather than mined as the natural

potential of the coke which, in turn, determines to a

2.2. Manufacturing process

Table 1 graphitized over 2500C, low porosity,

Fig. 3. Change in interlayer spacing of graphite with tempera-

Material Bulk density, g/cm 3 Temperature, K Pressure, atm

Pyrolytic carbon 1.2-2.2 2000 1.31 X 10-l°

3.3.3. Thermal conductivity

Temperature (T), Cp, H To - H oo S°

13 0.0080 0.0421 0.0041 0.0009

298 2.07 0 1.37 1.37

3000 C is shown in figs. 8 and 9, which illustrate that

3.3.4. Thermal expansion

• Flash Dlffuslvity MNsurments

3.4. Electrical properties

Final Term to be added to CTE

Spectral Integrated emissivity

Polished 0.803 -0.249 0.495 12.2 0.448 13.8

The strength of graphite is higher in the direction

peratures. Increases in strength of up to 30% have

at 2760 C, increased the room temperature ultimate Oxit~tlon,

strength from 25,800 to 81,700 psi [31], A 50% re-

easily at high temperatures. Creep in graphite is de-

3.5.5. Coefficient of friction at liquid-nitrogen temperatures. Surface areas calcul-

Material Test Atmosphere Coefficient of friction

Table 9 Gases other than water vapor or the gaseous pro-

Graphite Gas evolved to 1000 C, Gas evolved to 1800C, Constituents, v/o

coatings, reduces the permeability to gases by a factor

Irradiation effects have been investigated in many

and fluences. Most nuclear graphites are formed by ex- 0

and transverse to the axis o f extrusion. Dimensional

Fig. 23. Radiation-inducedlength changes of CSF (parallel)

Iilm"UPJC ~ ' " - - Y

Fig. 22. Radiation-induced length changes of CSF (transverse)

materials having a high CTE. However, the properties

0.29 NOIJ- .... 0

Fast Neutron Fluencl, 1021Ntutrons/cm2 (t>O. 18Mev) ~0

graphites show little change in CTE before turnaround

/.~.~x.~ 9~-1275 C • 300-375 o 7B-~5

100 pore structure, particle size, temperature, pressure,

Table 11 oxidation rate with temperature is observed for the

C + 0 2 =CO2 C + ~O2 = CO C + O =CO C + H 2 0 = C O + H2 C + 2 H 2 0 = CO2 + 2H2 CO + ]-]2° = CO2 + H2

CO + O = CO2 C+O3=CO+O2 C + C O 2 = 2CO 4CO = CO2 + C 3 0 2 C+OH=CO+H C + 2H2 = CH4

Fig. 39. CSF graphite oxidation data [16].

× exp(-49.86 X IO3/RT) (po2)0.5,

where PO2 is in atmospheric units, T is in degrees Kel-

Secondary reactions are

The rate equation is of the form

mined by the relative magnitudes of the terms in the

tiveness of hydrogen as an inhibitor also decreases. At

of the metal halides [72]. The coating temperature and

c 6.1. Reactions with metals

Metal Temperature, C Product or effect Oxide Temperature, C

You might also like