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C
Atomic number 6 12.011 Atomic weight
Number of neutrons: 6, 7, 8
Classification: Non-metal
Crystal structure: Hexagonal
Carbon Cubic
Crystal structure 4 Common oxidation state Density @ 293 K: Graphite 2.26 g/cm3
Diamond 3.53 g/cm3
Figure 1-1. Carbon as on the periodic table Color: Black, gray
In 1961, the International Union of Pure and Applied The history of manufactured graphite began at the
Chemistry (IUPAC) adopted the isotope 12C as the end of the 19th century with a surge in carbon manu-
basis for atomic weights. Carbon-14, 14C, an isotope facturing technologies. The use of the electrical
with a half-life of 5730 years, is used to date such resistance furnace to manufacture synthetic graphite
materials as wood, archeological specimens, etc. led to the development of manufactured forms of car-
Carbon-13, 13C, is particularly useful for isotopic label- bon in the early part of the 20th century and more
ing studies since it is not radioactive, but has a spin recently, to a wide variety of high-performance materi-
I = 12 nucleus and therefore a good NMR nucleus. als such as carbon fibers and nanotubes (Figure 1-2).
Carbon has four electrons in its valence shell (outer Forms of Carbon
shell). The electron configuration in carbon is 1s2 2s2
2p2. Since this energy shell can hold eight electrons, Carbon is found free in nature in three allotropic
each carbon atom can share electrons with up to four forms: amorphous carbon, graphite and diamond.
different atoms. This electronic configuration gives More recently, a fourth form of carbon, buckminster-
carbon its unique set of properties (Table 1-1). Carbon fullerene, C60, has been discovered. This new form
can combine with other elements as well as with itself. of carbon is the subject of great interest in research
This allows carbon to form many different compounds laboratories today. Within the past few years, this
of varying size and shape. research has centered on graphene and its derivatives,
which have the potential to bring about a fundamental
Carbon is present as carbon dioxide in the atmosphere change in the semiconductor/electronic industry.
and dissolved in all natural waters. It is a component
of rocks as carbonates of calcium (limestone), magne- Carbon alone forms the familiar substances graphite
sium and iron. Coal, petroleum and natural gas are and diamond. Both are made only of carbon atoms.
chiefly hydrocarbons. Carbon is unique among the ele- Graphite is very soft and slippery, while diamond is
ments in the vast number of varieties of compounds it one of the hardest substances known to man. Carbon,
can form. Organic chemistry is the study of carbon and as microscopic diamonds, is found in some meteorites.
its compounds. Natural diamonds are found in ancient volcanic
pipes such as found in South Africa. If both graphite
and diamond are made only of carbon atoms, what
gives them different properties? The answer lies in
the way the carbon atoms form bonds with each other.
Pre-1880
Lampblack (writing)
Charcoals (gunpowder, medicine, deodorants)
Natural graphite (writing material)
18801940
Activated carbons
Carbon blacks 109
1.54
Coal coking (coal-tar pitch)
Delayed coking
Synthetic graphite and diamond
3.58
1940-2013
Carbon fibers (PAN) Figure 1-3. The crystal structure of diamond
Carbon fibers (pitch-based) The forces within and between crystallites deter-
Carbon fibers (microporous) mine the extreme difference in properties between
Carbon/resin composites these two forms. In diamond, the crystal structure
is face-centered cubic (Figure 1-3). The interatomic
Carbon/carbon composites
distance is 1.54 with each atom covalently bonded
Specialty activated carbons to four other carbons in the form of a tetrahedron.
Carbon as a catayst support This interatomic distance is close to that found in
aliphatic hydrocarbons, which is in distinction to
Carbon whiskers/filaments
the smaller 1.42 carbon-carbon distance found in
Prosthetics graphite and aromatic hydrocarbons (1.39 in ben-
Intercalation compounds zene). This three-dimensional isotropic structure
Graphite/oxide refractories
accounts for the extreme hardness of diamond.
Pyrolytic carbon
700
Glassy carbon Solid
III
Mesocarbon microbeads
Diamond films 600
Diamond-like films
Elastic carbon 500 Diamond
Fullerenes
Pressure (kiloatmospheres)
Nanotubes
400 Liquid
Nanorods
Graphene
300
100
Gr.
Graphite and
metastable diamond
0
0 1000 2000 3000 4000 5000
T, K
1 Adapted from Marsh, H. et al., Introduction to Carbon Technologies,
(1997), pp. 4, 521. Figure 1-4. The carbon phase diagram
Thermodynamically, graphite at atmospheric pressure a given plane also provides the electron bond network
is the more stable form of carbon. Diamond is trans- responsible for the high mobility (electronic) of graph-
formed to graphite above 1500C (Figure 1-4). ite. This would appear more correct, since van der
Waals forces are the result of dipole moments, which
would not account for the high mobility.
A Consequently, weak forces between layer planes
account for (a) the tendency of graphitic materials
c
to fracture along planes, (b) the formation of intersti-
6.70 tial compounds and (c) the lubricating, compressive
and many other properties of graphite.
B
As previously mentioned for the hexagonal graphite
d
3.35 structure, the stacking order of planes is ABAB, so
that the atoms in alternate planes are congruent
A (Figure 1-5). Studies have shown that natural graphite
a contains 17 to 22 percent of a rhombohedral structure
1.42
with a stacking sequence of ABCABC. In artificial or
2.46 synthetic graphite, in the as-formed state, only a few
percent at best could be found. However, deformation
processes such as grinding substantially increase the
Figure 1-5. The crystal structure of graphite
percent of rhombohedral structure found in the other-
wise hexagonal structure.
The structure of graphite consists of a succession
of layers parallel to the basal plane of hexagonally Amorphous carbon is also referred to as nongraphitic
linked carbon atoms. The ideal graphite structure carbon. When examined by X-ray diffraction, these
is shown in Figure 1-5. materials show only diffuse maxima at the normal
scattering angles. This has been attributed to a ran-
In this stable hexagonal lattice, the interatomic
dom translation and rotation of the layers within
distance within a layer plane, a, is 1.42 and the
the layer planes. This disorder has been called tur-
interlayer distance, d, between planes is 3.35 .
bostratic. Some of these nongraphitic carbons will
Crystal density is 2.266 g/cm3 as compared with
become graphitic, upon heating to 17003000C.
3.53 g/cm3 for diamond. In the graphite structure
Some will remain nongraphitic above 3000C.
(sp2 hybridization), only three of the four valence
electrons of carbon form regular covalent bonds Thus far, the discussion has centered on the crystal
(-bonds) with adjacent carbon atoms. The fourth structure of graphites. On a more macroscopic level,
or electron resonates between the valence bond the structure as routinely examined on a light micro-
structures. Strong chemical bonding forces exist scope at magnifications of 100, 200 and 500 times
within the layer planes, yet the bonding energy reveals the porosity, particle or grain size and the
between planes is only about two percent of that general microstructure as it is commonly referred to.
within the planes (150170 kcal/[gram atom] vs. Photomicrographs of POCO AXF-5Q graphite compared
1.34 kcal/[gram atom]). These weaker bonds to a conventional graphite demonstrate some signifi-
between the planes are most often explained to cant differences when viewed at 100 magnification
be the result of van der Waals forces. (Figure 1-6) and at 500 magnification (Figure 1-7).
It can be seen from these photos that vast differences
However, Spain2 identifies the orbital, which has a pz
do exist in graphite microstructure. These differences
configuration, and not van der Waals forces as the cor-
are directly related to raw material and processing
rect source of bonding between the adjacent layers. In
parameters.
general, the bands overlap by ~40 meV to form the
three-dimensional graphite network where the layer As seen in the photos, the dark or black regions repre-
planes are stacked in the ABAB sequence illustrated sent the porosity while the lighter regions represent
in Figure 1-5. Spain concludes in his discussions on the graphite matrix. It is this matrix, composed of
electronic structure and transport properties of graph- smaller particles bound together either chemically
ite that the overlap of orbitals on adjacent atoms in or mechanically, which is comprised of the crystals
stacked layer upon layer. This is more easily seen in
2 Spain, I.L., Electronic Transport Properties of Graphite, Carbons, scanning electron micrographs (SEM).
and Related Materials, Chemistry and Physics of Carbon, 16 (1981),
p. 119.
Test Methods
The structure of graphite has been determined
through such methods as X-ray diffraction, transmis-
sion electron microscopy, neutron diffraction and
convergent beam electron diffraction. These methods
are highly sophisticated and generally require very
expensive equipment with a highly skilled operator.
This is normally beyond the scope of typical industrial
laboratories. Since this type of testing or analysis is
POCO AXF-5Q Graphite mag. 500
more research-oriented, no standard methods will be
presented.
However, several books have been published on the
structure of graphite and the reader is encouraged to
review the bibliography in the appendix.
POCO graphites are also highly isotropic with respect Conversely to the interlayer spacing, d,
to their structure and properties. The isotropy factor is the crystallite size, La, begins a sharp increase about
between 0.97 and 1.03 with 1.00 being perfect. A factor 1500C and continues to about 2000C where it begins
of 1.00 means the properties are identical no matter to level off. The size at <1500C is 50 and increases
which direction they are measured in. Many conven- to about 400 at 2000C.
tional graphites are anisotropic. This means the
A difference will be noted in petroleum coke versus
properties vary depending on which direction you
pitch coke. The pitch coke does not increase to the
test them in. The high degree of isotropy makes POCO
same size as the petroleum coke at the same tempera-
graphites useful in many applications where an aniso-
ture. It parallels about 75 lower, beginning about
tropic material would fail. It also allows for maximum
17001800C. La is the basal plane size. La, which also
utilization of material, as machining orientation is of
increases, is the stacking direction height (Figure
no importance.
1-5). The total size increases while the interlayer
spacing, d, decreases. These changes, along with
Temperature Effects processing parameters, account for the excellent prop-
There are two general types of carbon, those consid- erties of petroleum coke-based graphite
ered to be graphitizing carbons and those that are
nongraphitizing. The most significant difference is Density Effects
found in the apparent layer size and apparent stack
Isotropy is independent of density. A high- or low-
height. For equal layer sizes, the apparent stack
density material can be isotropic or anisotropic.
height, i.e., average number of layers per stack, is less
The general crystal structure is also independent
for nongraphitizing carbons than graphitizing carbons.
in that the greatest effects on density are due to pro-
The layer stacking is more perfect in graphitizing car-
cess parameters. The same crystal structure can
bons than nongraphitizing. These apparent sizes and
exist independent of the density of the bulk piece.
heights are important in the first stages of
carbonization.
1100K
1500K
Apparent Density
1700K
Definition
2000K
The density of a substance is the amount of material, or
mass, per unit volume. Density is ordinarily expressed
in grams per cubic centimeter or pounds per cubic
foot (1 g/cm3 = 62.4 lb/ft3). To determine the density
of a specimen, one would first calculate its volume
from the physical dimensions (for a rectangular solid,
the volume is equal to the product of the length, width
and thickness). Next, the mass would be determined
by weighing the specimen. The density is determined
by dividing the mass by the calculated volume.
Figure 1-9. A model of changes from mesophase to graphite during If the specimen were completely homogeneous, with
heat treatment 3 no flaws or voids, this method of determining density
The structure of graphite with regard to interlayer would yield the theoretical value. Graphite materials
spacings and crystallite size does change with temper- are, however, porous; hence, the term apparent
ature (Figure 1-9). Interlayer spacing, d, decreases as density.
heat-treat temperature increases. Beginning at about In general, the differences in density of POCO graph-
1500C, the interlayer spacing, d, decreases sharply ites reflect what some of the other physical properties
from about 3.50 to about 3.40 when the tempera- will be. The higher-density graphite will, generally, be
ture reaches 2000C. At this point it begins to level off, stronger with a higher hardness value plus improve-
approaching 3.35 above 3000C. The crystallite size, ment in many other properties and characteristics.
La, increases as heat-treat temperatures increase.
3 See footnote 1.
The mathematical expression for the determination of porous, the intrusion of water into the porosity is slow
density is: and the accuracy with this method is 1 percent if the
W submerged weight is taken quickly.
D= W = 7.500 g + 1.831 g/cm3
D=
V The general steps
V in4.097
the water
cm3 method are as follows:
Where: D = Density in g/cm3 1. Support the piece of graphite by a thin wire/thread
W = Weight of specimenW in grams and weigh the piece of graphite in air.
D=
V = Volume of specimen
V in cm3 2. Submerge the piece in a container of water in
Or, if the weight is expressed in pounds and the vol- such a way that the submerged weight can be
ume is expressed in cubic feet, then the density would determined.
W
be in units
V = lof pounds
w t = 1.000
= 0.5000
perDin
cubic foot.in 0.5000 in 3. Calculate the density by the following formula:
V
V = 0.25 in3
Sample Calculation: W
D= DL
W1W2
A graphite
V = lspecimen has a length (l) of 1.000 inches,
w t = 1.000 in 0.5000 in 0.5000 in
a widthV(w) andinthickness
= 0.25 3 (t) of 0.500 inches, and Where: D = Density in g/cm3
a weight of 7.500 grams. Calculate the apparent W = Weight (in grams)
density (D). W1 = Weight in air (in grams)
V = l w t = 1.000 in 0.5000 in 0.5000 in W2 = Weight in water (in grams)
V = 0.25 in3 DL = Density of water
W 7.500 g + 1.831 g/cm3
D= =
4.097 cm
To convert to cmV3, multiply
3
by 16.387 (1 inch = POCO Graphites vs.
Pr =Conventional
2 cos Graphites
2.54 cm, Appendix A).
POCO graphites are manufactured in a variety of
W 7.500 g + 1.831 g/cm3 grades covering the density range from 1.30 g/cm3
D= =
V 4.097 cm3 to 1.88 g/cm3. The density is a particularly important
characteristic of graphite because, in addition to its
Test Methods inherent significance, it has a direct influence on
W = 7.500 g + 1.831 g/cm3 other properties. Generally, theV maxphysical and mechani-
D=
The standard method
V 4.097commonly
cm3 used to determine S = as
cal properties improve the density
0.0225 PdV is increased;
the apparent density of graphite
W is described in details will be presented in later sections. Commercial,
ASTM Standard C559 D =and Research
DL & Development 0
W1W2 polycrystalline graphites seldom exceed 80 percent of
Analytical Services Laboratory Instruction (TDI) the theoretical density figure (2.26 g/cm3) due to voids
4.1.1.1 (Appendix B). and pores. Single crystal and pyrolytic graphites,
W
D = such asthe
For premium graphites, DL POCO grades, an because of their highly ordered structures and absence
W1W2
alternate method of determining apparent density is of pores, have densities closely approaching the theo-
the water method. This is a method that can be used retical value. In comparison toL most other materials of
C.S. a= low density (Figure 2-1).
construction, graphite has
on objects of irregular shapeW where the volume would A
D = Even though
be difficult to calculate. DL the graphite is This is a decided advantage for some applications.
Pr =W2
1Wcos
2
25
20 Pr = 2 cos
L 3500 lbs 14,000 psi
C.S. = = =
A 0.25 in2
Density, g/cm3
15
V max
S Pr = 2 cos
= 0.0225 PdV
10
0
V max
5 S = 0.0225 PdV
0
0
Rubber ABS/PVC *Graphite: Graphite: Aluminum Silicon Alumina Steel Brass Copper Nickel Tungsten Gold Platinum
V max
Plastic Poly-
S =crystalline
0.0225 LPyrolitic Carbide Carbide
C.S. = PdV *synthetic/manufactured graphite
A
Figure 2-1. Typical densities of various0 engineering materials
L
POCO GRAPHITE, INC. C.S. = PROPERTIES AND CHARACTERISTICS OF GRAPHITE 7
A
POROSITY
Temperature Effect pressure and volume filled, the pore size and pore
volume can be determined. There are certain disad-
The apparent density will be influenced by tempera- vantages of this method, such as:
ture during the graphitization process. Generally, the
higher the graphitization temperature, the higher the 1. The pores are not usually circular in cross-section
density will become. There are other factors which and so the results can only be comparative.
may contribute to this also, but there is an appreciable 2. The presence of ink-bottle pores or some other
density increase as you go from 2000C to 3000C. shape with constricted necks opening into large
void volumes. The pore radius calculated by the
Washburn equation is not truly indicative of the
Porosity true pore radius and capillaries are classified at
too small a radius.
Definition 3. The effect of compressibility of mercury with
The standard definition for porosity, as found in ASTM increasing pressure. This should be corrected for
Standard C709 which has definitions of terms relating by carrying out a blank run.
to manufactured carbon and graphite, is the percent- 4. The compressibility of the material under test. This
age of the total volume of a material occupied by both is a problem of particular importance for materials
open and closed pores. When one calculates the which have pores that are not connected to the sur-
apparent density of a material, the pore volume is face, e.g., cork. Additionally, pore walls may break
included in the calculation. This results in typical under the pressures used if the material under test
maximum densities for nonimpregnated manufactured is relatively weak. This could cause a bias in the
graphites of 1.90 g/cm3. The theoretical density of data.
graphite is 2.26 g/cm3. This means that in the very best
case, about 16 percent of the volume of a bulk piece of 5. The assumption of a constant value for the surface
graphite is open or closed pores. This porosity plays an tension of mercury.
important role in many ways, as will be discussed later. 6. The assumption of a constant value for the angle of
contact of mercury.
The characteristics of the porosity of POCO fine-
grained graphites have been studied extensively.4 30
Closed Porosity (% of Theoretical)
25
Test Methods
20
There is no recognized ASTM standard for measuring
the porosity of manufactured graphites at this time. 15
A number of techniques may be employed for the pur- 10
pose and are widely in use today. It is important to
state the method by which porosity data is determined 5
because each method imparts its own bias. 0
1.5 1.6 1.7 1.8 1.9
One of the more widely used methods is mercury poro- Apparent Density (g/cm3)
simetry. Two other methods in use are gas absorption
by the BET technique and direct image analysis of the Figure 3-1. Closed porosity vs. density
microstructure. The latter is gaining increased accep- 1.1
tance as a means of measuring more accurately the 1.0
real pore structure. The advent of computer and video 0.9
Average Pore Diameter (m)
100 10,000
90 POCO
graphite
80
Conventional
graphite 1000
70
60
50
100
AXF-5Q
40
30
20 10
ZXF-5Q
10
0
0.01 0.1 1 10
1
Pore Diameter (microns) 20 40 60 80 100 120 140 160
Pressure (psi)
Figure 3-3. % distribution of open porosity: POCO graphite vs. All test samples: 1/4 thick
conventional graphite Flow cross section: 1.25 diameter
The fineness of the porosity allows POCO materials to Figure 3-4. Helium flow vs. pressure for some POCO graphite
be modified to create truly impermeable graphite. materials
With various post-processing techniques, POCO can 5
seal, fill or close the porosity, depending on the end
application. The high degree of open porosity also
allows Entegris to purify the material to less than
4
5 parts-per-million (ppm) total impurities, by ash
analysis. Figure 3-4 shows helium flow data on various
Cumulative Weight Pick-up (%)
AXZ-5Q
grades of POCO graphite. It clearly shows a wide vari-
3
ety of capabilities for POCO graphites. The helium flow
test for checking the permeability, like the mercury
porosimetry test, has its limits or bias and should be
clearly identified when using data generated by it. 2
Permeability is simply the rate of flow of a medium
such as a gas or liquid through a material while under
a pressure gradient. The pores of POCO graphite are 1
AXF-5Q
not only uniformly distributed, but are well intercon-
nected so flow can take place through them. There are ZXF-5Q
applications (such as filters) where this is important. 0
0 24 48 72 96 120 144 168 192
Another feature of the small pore size is that some liq- Soak Time in Water (hours)
uids will not generally penetrate the pores readily. For
instance, it has been determined that after soaking in Figure 3-5. Water absorption of POCO graphites
water for seven days, a sample of AXF-5Q picked up
less than one percent by weight of the water (Figure
3-5). This could be an advantage in some applica-
tions. However, in other applications, such as wanting
to infiltrate a liquid such as molten copper, very high
pressures are required at high temperatures to accom-
plish it. This is a decided disadvantage.
80
POCO Graphite vs. Conventional Graphites
78
Since hardness is influenced by a number of other fac-
Shore Scleroscope Hardness (SSH)
Temperature Effects 66
ACF-10Q ACF-10QE2
Identification Notched Unnotched Notched Unnotched
1 0.095 0.748 0.107 0.721
2 0.084 0.479 0.108 0.708
3 0.078 0.597 0.112 0.570
4 0.081 0.371 0.113 0.639
5 0.086 0.430 0.104 0.598
6 0.091 0.690 0.105 0.780
7 0.539 0.681
8 0.558 0.612
9 0.652 0.650
10 0.503 0.788
11 0.650
Group Ave. 0.086 0.565 0.108 0.675
These results are based on the tests performed and are subject to change upon the receipt of new or additional information.
COMPRESSIVE STRENGTH
W
D=
V
V = l w t = 1.000 in 0.5000 in 0.5000 in
V = 0.25 in3
TABLE 6.3: SUMMARY OF RESULTS To convert to MPa, multiply by 0.0068948.
Density Effects
Support span
As with many other properties, the compressive Roller
pin
strength of graphites changes with apparent density;
the higher density having the highest strength LL
(Figure 7-2).
Cross section of specimen
30
28
T
26
24 W
Compressive Strength (ksi)
22
Figure 8-1. Four-point loading fixture
20
18
16
The mathematical expression for calculating flexural
14
strength is:
12 PL
F.S. =
10 W(T)2
8
Where: F.S. = Flexural strength in pounds per square inch
6 (psi)
1.56 1.60 1.64 1.68 1.72 1.76 1.80 1.84 1.88
P = Load in pounds at failure
Apparent Density (g/cm3)
L = Length between outer support roller pins
Figure 7-2. Compressive strength of the graphite changes when in inches
apparent density increases W = Width of specimen in inches
PL 500 3.0 lbs 1500
F.S. = T 2==Thickness of specimen
=PL in inchespsi = 8000 psi
W(T) F.S. =2 0.1875
0.75 (0.50) in2
Flexural Strength Sample Calculation:
W(T)2
P/A PLo
E= =
FLEXURAL STRENGTH
are comparable to those obtained with the fixture The probability of detecting the largest flaw in the
recommended by ASTM. Regardless of the procedure specimen during 3-point loading is minimized since
followed, steps must be taken to avoid factors that bias the largest flaw must be at the surface and along the
the results, such as improper sample alignment, rough line of peak stress. Consequently, the specimen frac-
and/or non-parallel surfaces. It is also important to tures at either a smaller flaw or within a region of
know whether the reported strength values were lower stress, thus yielding artificially higher strength
obtained from three-point or four-point loading. values in comparison with 4-point loading results. The
strength limit of the material, or even the local stress
For example, a test specimen typically has a uniform
and flaw size that caused fracture, is not revealed in
rectangular cross-section but the load may be applied
3-point loading. It only indicates the peak stress on
in three or four point as illustrated in Figure 8-2. Note
the tensile surface at the time of fracture for a given
the shaded areas indicating the stress distribution. In
material.
3-point loading, the peak stress occurs on a single line
at the surface of the test bar and opposite the point of
loading. The stress decreases linearly along the length POCO Graphites vs. Conventional Graphites
of the bar, and into the thickness of the bar, until In a brittle material such as graphite, the flexural
reaching zero at the bottom supports. strength is particularly sensitive to flaws or defects
in the material. If a flaw is present within span L,
Unlike the 3-point bend tests, where the peak stress
i.e., between the outer support pins of the flexural
occurs on a single line opposite the point of loading,
test specimen, then the load P required to break the
4-point loading distributes the peak stress over an
sample will be reduced. When failure occurs, it is cata-
area that is determined by the width of the sample
strophic. The sample breaks suddenly and, frequently,
and the span of the top loading supports, respectively.
small chips and flakes of material break away at the
Observe how the tensile stress distribution decreases
point of failure.
linearly from the area of peak stress on the tensile
face, and into the thickness of the bar, until reaching POCO graphites have flexural strengths covering the
zero at the bottom span supports. The increased area range from 34 MPa (5000 psi) to over 124 MPa (18,000
and volume under peak tensile stress, or near the psi). These values are quite high when compared to
peak tensile stress, in 4-point loading increases the conventional graphites, which may range from less
probability of encountering a larger flaw. than 7 MPa (1000 psi) to around 41 MPa (6000 psi).
The fine particle size and homogeneous structure
Load
of POCO graphites contribute to their high flexural
strengths. Another important characteristic of this
property in POCO graphites is that the flexural
3-point Flexural Test
strength is the same for samples cut from any direc-
tion or orientation of the parent block of material.
This characteristic is called isotropy; POCO graphites
are said to be isotropic, whereas most other graphites
are anisostropic. In conventional graphites that are
molded or extruded, the ratio of flexural strengths
Peak stress
between the against grain and with grain directions
may range from 0.3 to 0.5.
Peak stress
Density Effects point. Since the stress at this point is higher than the
overall average throughout the specimen, a crack will
Flexural strength, like many other physical properties begin to propagate and premature fracture will occur.
of graphite, increases with increasing density. For To alleviate this situation, carefully machined, highly
example, nominal flexural strength of 5 micron polished specimens are used. Also, of no importance is
graphite (AXF-5Q, AXM-5Q and AXZ-5Q) ranges from the alignment of the gripping PLapparatus on the speci-
600017,000 psi for densities of 1.60 (g/cm2) and F.S. =
men. Even small misalignments
1.88 (g/cm2), respectively (Figure 8-3). W(T)2could cause
premature fracture, resulting in an erroneous (low)
value for the tensile strength.
24
22
Tensile strength, like compressive strength, is
expressed in pounds per square inch and is calcu-
20
lated in the same manner as compressive strength,
18 i.e., the applied force at failure is divided by the
16 cross-sectional
PL
= area of the sample.
500 3.0 lbs 1500
Flexural Strength (ksi)
0
To convert to MPa, multiply by 0.0068948.
1.56 1.60 1.64 1.68 1.72 1.76 1.80 1.84 1.88
Apparent Density (g/cm3) Tensile strength = 55 MPa
9000
Temperature Effects
As the testing temperature of graphite is increased,
its tensile strength increases; this is in sharp contrast
to the behavior of metals, which show a decrease in 8000
strength as temperature increases. In an inert atmo-
Tensile Strength (psi)
14,000 F.S. =
W(T)
PL
2
W
60 F.S. =
12,000 W(T)2
Single
Al2O3 crystal
50 graphite
10,000
Mo
Tensile Strength (psi)
TiC
2000
Al
10 Load 2000 lbs
Phenolicstrength =
Tensile =
SiO2 glass =Polycrystalline
8000 psi
0 plastic Area
Load 0.25 in
2000
2
lbs graphite
1.60 1.64 1.68 1.72 1.76 1.80 1.84 1.88
0
Tensile strength =
NaCl = = 8000 psi
Apparent Density (g/cm3) Area
Load 0.25 in
2000
2
0
Tensile 500 1000= 1500
strength =
2000 2500lbs 3000
= 8000 3500psi 4000
Figure 9-3. Nominal tensile strength vs. apparent density of POCO Area
Melting Point0.25
(C) in
2
Modulus of Elasticity T
= E = Constant
eT
Definition = E = Constant
The elasticity of a material is related to a uniformly Where: T = Stress eT
= =
increasing separation between the atoms of that mate- e = Strain e E Constant
E = Modulus of elasticity, or Youngs modulus
rial. As a consequence, the elasticity is directly related
to the bonding between atoms and the respective Stress is the load per unit area and strain is the ratio
energies associated therewith. This can be readily of change in length to
T =the original
e = length, i.e.,
P L
demonstrated by showing the general relationship A
P Lo
L
between modulus of elasticity (MOE) and melting T= e=
A
P Lo
L
points of various materials. The higher the melting T= e=
point (i.e., the energy required to disrupt the atom- Where: P = Load A Lo
to-atom bonds), the higher the modulus of elasticity A = Area
(Figure 10-1). The presence of a second phase of dif- L = Change in length (L Lo)
fering modulus results in most of the stress being Lo = Original length P/A PL
E= = o
carried by the higher modulus phase. Porosity, which L / L
P / Ao PL L
Therefore: E= = o
is uniformly distributed and continuous, constitutes a
second phase. The effect on the modulus in materials P // ALo PL
L L
E= = o
of less than 50 percent pore volume can be repre- L / Lo L
sented by the relationship:
P/A PL
E= = o
L / Lo L
Sample Calculation: TABLE 10-1. MODULUS OF ELASTICITY OF
VARIOUS GRAPHITES
If a tensile sample with a diameter of 0.220 inch and a
gage length of 1.000 inch breaks at 500 pounds with a Apparent MOE
gage length increase of 0.008 inch, the tensile MOE Material Density (g/cm3) (106 psi)
would be 1.6 106 psi. POCO AXZ-5Q 1.65 1.3
PLo (500 lbs)(1) AXM-5Q 1.72 1.5
E= = = 1.6 106 psi
L A (0.008 in)(0.038 in2) AXF-5Q 1.77 1.6
The modulus of elasticity is usually expressed in Mersen 2161 1.66 1.3
millions of pounds per square inch (106 psi), or in 2020 1.77 1.3
N/mm2 in metric units. 2080 1.87 1.8
Density Effects
The density relationship is evident with about a
15 to 20 percent increase in modulus detected as
the density increases from 1.65 g/cm3 to 1.77 g/cm3.
This follows the same pattern as other strength
properties for graphite.
Electrical Resistivity
E=
P/A
L / L
=
PL
L
o
TABLE 11-1. TYPICAL ELECTRICAL RESISTIVITY OF
VARIOUS MATERIALS*
P o L
T= e= Electrical
Definition A Lo
Resistivity
The electrical resistivity is that property of a material Material** Range (-in) Comments
which determines its resistance to the flow of an POCO graphites 4501000 Polycrystalline graphite
electrical current and is an intrinsic property. The Toyo Carbon 300600 Polycrystalline graphite
electrical resistance of a substance is directly propor- graphites
PLo (500 lbs)(1)
tionalEto= the length
= of theP /current
A inPL path,
= 1.6i.e.,
10as6 psi
the
L A (0.008
E = in)(0.038= 2)o increases. It is Mersen graphites 5501200 Polycrystalline graphite
current path increases, the resistance
L / Lo L
also inversely proportional to its cross-sectional area, Toyo Tanso USA 400500 Polycrystalline graphite
i.e., as the area increases, the resistance decreases. graphites
The mathematical expression for the determination Copper 1.11.5 Pure, wrought
of electrical resistivity is: Gold 0.9 Pure
AR Silver 0.6 Pure
ER =
PL L
(500 lbs)(1)
E= o = = 1.6 106 psi Tungsten 2.2 Pure
L AElectrical
Where: ER = (0.008resistivity
in)(0.038atin2room
) temperature Carbon steels 7.17.5 Hardening grades,
A = Cross-sectional area (square inches) wrought
R = Electrical resistance of the material (ohms)
(0.25 in2)(0.00425 ) Stainless steel 15.728.3 400 series, wrought
ER = between potential contacts (inches)
L = Distance
2.0 in Cobalt base 36.674.3 Wrought
Sample Calculation: superalloys
AR
ER =a cross-sectional area of
For a graphite sample with Nickel base 3.052.4 Wrought and cast
L superalloys
0.25 in , distance between the potential contacts of
2
Thermal Expansion
700
650
Definition
600 The physical dimensions of a body are determined by
the number and spacing of its atoms. At temperatures
Electrical Resistivity (in)
1200
Where: CTE = Coefficient of thermal expansion
L = Change in sample length from the lower
1100 temperature to the upper temperature
1000 L = Sample length at the lower temperature
T1 CTE
= Lower 2.0164 in 2.0000 in
= temperature
Electrical Resistivity (in)
900
T2 = Upper2.0000 in (1000C
temperature seenby
23C)
sample
800
Test Method 10
QX
K=
Thermal Conductivity Sample Calculation: AT
Assume a flat plate of graphite 0.1 foot thick has a sur-
Definition face area of one square foot. Heat is flowing through
this plate at a rate of 1000 Btu per hour; the hotter
The thermal conductivity of a material is a measure surface is at a temperature of 1036F, while the cooler
of its ability to conduct heat. A high thermal conduc- surface is at 1018F; calculate the thermal
tivity denotes a good heat conductor, while a low conductivity.
thermal conductivity indicates a good thermal
QX (1000 Btu)(0.1 ft)
insulator (Table 13-1). K= =
AT (hr)(1 ft2)(1036F 1018F)
TABLE 13-1. TYPICAL THERMAL CONDUCTIVITY OF
(1000 Btu)(0.1 ft) 55.5 Btu-ft
VARIOUS MATERIALS K= =
(hr)(1 ft2)(18F) hr/ft2 F
Thermal Conductivity Range
Material Btu-ft/hr/ft2 F To convert to metric system of units, multiply by 0.413
Natural rubber 0.082 to obtain:
Nickel 650 K = 22.9 cal/(meter C sec)
Steel (wrought) 821 To convert to SI system of units, multiply by 1.73 to
Silicon carbide 925 obtain:
Tungsten carbide 1651 K = 96.0 W/m-K
Brass 15135 K = CP
Test Method
Iron (cast) 2530
POCO graphite
L
CTE = 4070 Historically, two different techniques were employed
L(T2T1) for determining thermal conductivity over the
Platinum 42 temperature range of 1103300 K. They are:
Conventional graphite 6595
1. A comparative rod Rapparatus
(1)from 110 K to 1250 K
=
Aluminum 67135
2. A radial inflow apparatus E
from 1250 K to 3300 K
Tungsten 97
2.0164 in 2.0000 in There is no standard method associated with graphite
Copper CTE = 112226 for measurement of thermal conductivity.
2.0000 in (1000C 23C)
Gold 172 However, ASTM Standard C714-72 is routinely
Silver 242 used for determining thermal diffusivity and the
(1)K
= used
corresponding resultsR'are E to calculate thermal
The mathematical expression for thermal conductivity conductivity. POCO graphite deviates from ASTM
(K) is: Standard C714-72 in that this standard requires the
QX use of a flash lamp for sample heating and thermocou-
K= ples for monitoring temperature. A similar technique
AT
employed by POCO utilizes a Netzsch LFA-427 (Laser
Where: Q = Rate of heat flow through a slab in Btu Flash Apparatus), which hasKTa high-intensity laser to
S
= the
heat the sample surfaceR andET resultant temperature
per hour
A = Cross-sectional area of the slab in feet2 change is monitored with an infrared detector (Figure
X = Thickness of slab in feet 13-1).
T = Temperature drop across the slab (F)
Thermal diffusivity measurements involve quantifying
Therefore, K is expressed as: 0.29
the rate of diffusion of cal
heat through a703
cm kgwhere
solid
QX (1000 Btu)(0.1 ft) KT
local temperature cm 2
sec C cm 2
K= = Btu-ft/hr/ft2 F R= S
= and temperature gradients vary
AT (hr)(1 ft2)(1036F 1018F) with time. E T is a 8.4
This 10 advantage
decided
-6
0.112 in
10
thatkg
-6
thermal
or
diffusivity measurements cm
C are nonsteady-state,2
due to
(1000 Btu)(0.1 ft)C sec)
cal/(meter
55.5 Btu-ft
K= or = the transient nature of diffusion, thus eliminating
(hr)(1 ft2)(18F) hr/ft2 F cal
W/m-K R = 216.7
the need for determining heat flux and maintaining
cm sec
steady-state conditions. Nonetheless, close control
of local time-temperature relationships in the system
is required. Thermal diffusivity methods are also pre-
ferred over heat flux measurements due to the ease
K = CP
THERMAL CONDUCTIVITY
L
CTE =
L(T2T1)
1.2
2.0164 in 2.0000 in
CTE =
IR sensor ZXF-5Q
2.0000 in (1000C 23C) AXF-5Q
GE lens 1.0 TM
Iris diaphragm
QX
Sample holder K=
AT 0.4
Vacuum seal
Sample holder
adjustment 0.2
Enlargement optic
0.0
0 200 400 600 800 1000 1200 1400 1600 1800
Decoupling mirror Temperature (C)
Shutter
QX = (1000 Btu)(0.1 ft)
K=
AT (hr)(1 ft2)(1036F Resonator
1018F) Figure 13-2. Thermal diffusivity of POCO graphites
Adjustment laser
cal
R = 216.7
QX = (1000
QX Btu)(0.1 ft) THERMAL SHOCK
K= K= 2 (1)
AT (hr)(1 ft
AT)(1036F 1018F) R=
E
(1000 Btu)(0.1 ft) 55.5 Btu-ft
K= =
QX
(hr)(1 ft2)(18F) hr/ft2 F
K=
AT
T
K = Thermal conductivity POCO Graphite vs. Conventional Graphites
C cm2
= Coefficient of thermal
KTS expansion Some early studies10 reported that coarse-particle
R=
E = Modulus R =of216.7 ET cal
elasticity graphite had better thermal shock resistance than
cm sec finer-particle graphite despite the higher strength of
Another way to express this would be:
finer-particle graphite. The study further indicated a
KT correlation to the binder. If the binder were decreased,
R= S
0.29 cal E cmT 703 kg the thermal shock resistance also dropped, suggesting
KTS cm2 sec C cm2 the thermal stresses were being absorbed by the
= = Thermal
Where: RR = shock resistance
K =EThermal
T 8.4 10 -6
conductivity 0.112 10-6 kg binder material. Other studies11 have shown the pre-
TS = Tensile0.29 C
strength cm2 cursor material, e.g., tar coke versus oil coke, to have
cal cm 703 kg
= Coefficient of thermal expansion2 effects on the thermal shock resistance. The oil coke
KTS cm2 sec Ccal cm
E R =T = Tensile
= Rmodulus
= 216.7 -6
of elasticity had resistance values about seven times higher than
ET 8.4 10 cm sec0.112 10-6 kg
the tar coke.
This expression may be C a simpler form cm to 2use and
consequently will be used in the sample calculation.
cal
R = 216.7 9 Sato, S., Sato, K., Imamura, Y. and Kon, J., Carbon, 13 (1975),
cm sec p. 309.
10 Kennedy, A.J., Graphite as a Structural Material in Conditions of
High Thermal Flux. (Cranfield: The College of Aeronautics,
November 1959. [CoA Report No. 121]), p.15.
11 Sato, S., Hwaji, H., Kawamata, K. and Kon, J., Resistance and
Fracture Toughness Against Thermal Shock of Several Varieties
8 Kingery, W.D., Journal of the American Ceramic Society, 38 of Graphite," The 22nd Japan Congress on Materials Research
(1955), p. 3. Metallic Materials, Mito, Japan: March 1979, 67-68.
Generally, due to small particle size and high CTE, Density Effects
POCO graphite may not fare as well as some other
graphites in overall thermal shock resistance. Tests Since, generally, strength and thermal conductivity
at Entegris have shown that samples of the AXF-5Q increase with density, higher thermal shock resistance
grade, measuring one inch cubed, can survive a should be found in higher-density ranges. However,
1000C to 10C instantaneous change without fractur- with higher density, higher modulus and CTE are also
ing in repeated tests. Other tests on POCO graphites usually found and these would tend to offset the gains
have subjected the samples to 335F to -335F instan- in strength. The coarser-particle systems may be more
taneous changes without affecting the graphite. A effective than the finer-particle systems on an equal
comparison of some thermal shock resistance values density basis. Many factors are involved, and well
for some materials is shown in Table 14-1. defined tests to measure these effects are not in
common use.
TABLE 14-1. THERMAL SHOCK RESISTANCES
cal/cmsec Specific Heat
POCO graphite (AXF-5Q) 217
(ZXF-5Q) 233 Definition
GLC (Graphnol) 450 Heat capacity is the quantity of heat required to raise
Mersen graphite (2020) 140 the temperature of a unit mass of material 1, and the
relationship between the two most frequently used
Pyrolytic graphite (w/grain) 4300 units is as follows:
(a/grain) 0.29 Btu cal
1 =1
SGL Group, The Carbon (EK-82) 252 lb F g C
Company graphite
(EK-87) 426
It has been found that the values of heat capacity for
Titanium carbide (unknown) 3.45 all types of natural and manufactured graphites are
Toyo Tanso USA graphite (Isograph 88) 340 basically the same, except near absolute-zero tempera-
UCAR (ATJ) 329 tures. The differences found in measuring the same
grade of graphite are as great as the differences in
measuring WS ofDgraphite.
different =grades Differences
While the differences are not as great between the CP (graphite) S CP (sapphire)
as much as nine percent haveDbeen
W G G found between
various grades as the pyrolytic graphite shows between
natural graphite and manufactured graphite at low
orientations, it should still be noted that processing
temperatures (120 K to 300 K), but at higher tempera-
variables, starting materials, etc., can influence the
tures the differences for all types of graphite has been
thermal shock resistance of graphite. For example, the
found to be less than the experimental error. Table
Ringsdorff EK-87 grade has an average particle size
15-1 shows comparisons to other materials.
of 20 microns, yet it has about 30 percent more calcu-
lated thermal shock resistance than the UCAR ATJ,
Heat Capacity Equation
which has an average particle size of 25 microns and
nearly twice the calculated resistance of a POCO The heat capacity at constant
0.023 g pressure
40 (CP) can
cal be
CP (graphite) = 0.19
graphite with a particle size average of 4 microns. expressed by polynomial functions
0.077 g 52.5of the absolute
g C
temperature T, with T in K to give CP in cal/(gC).
cal J
Temperature Effects (graphite) = 0.382
Within theCPtemperature interval 0 K=to1.6300g K:
g C K
Depending on the type of graphite used and its partic-
ular characteristics or properties, and considering CP = (0.19210 x 10-4)T (0.41200 x 10-5)T2
shape, size, etc., higher temperature drops could be (0.10831 x 10-7)T3 (0.10885 x 10-10)T4
sustained without affecting the graphite. The tempera-
ture starting and ending points may have some bearing However, below 40 K, this equation has not been
on the overall resistance to fracture, because the reliable in correlation with experimental data. The
material will be thermally stressed differently at ele- calculated values are in good agreement (<2.2 per-
vated temperatures. A drop from 1000C to 500C may cent) with the experimentalWvalues
S,
for temperatures
respond differently than from 500C to 0C. Little data above 40 K. En, =
W BB,
is available to clearly define what the relationship or
limits are for the different types of graphite.
C 1 1
=
SPECIFIC HEAT
TABLE 15-1. TYPICAL SPECIFIC HEAT OF TABLE 15-2. TYPICAL SPECIFIC HEAT OF
VARIOUS MATERIALS MANUFACTURED GRAPHITES
Heat Capacity Heat Capacity Specific Heat Specific Heat
Material Range cal/(gC) Range J/(g K) Temperature (K) (cal/[gC]) (J/[g K])
Gold 0.031 0.13 0 0.0000 0.0000
Platinum 0.031 0.13 50 0.0101 0.0423
Tungsten 0.034 0.14 100 0.0335 0.1402
Tungsten carbide 0.04 0.17 150 0.0643 0.2690
Silver 0.056 0.23 200 0.0995 0.4163
Brass 0.090 0.38 250 0.1357 0.5678
Nickel 0.0910.14 0.380.59 300 0.1723 0.7214
Copper 0.092 0.38 350 0.2090 0.8750
Steel (wrought) 0.11 0.46 400 0.2450 1.0258
Iron (cast) 0.13 0.54 450 0.2760 1.1556
Graphite 0.17 0.72 500 0.3030 1.2686
Alumina 0.19 0.79 550 0.3230 1.3523
Aluminum 0.220.23 0.920.96 600 0.3400 1.4235
Silicon carbide 0.2850.34 1.191.42 650 0.3560 1.4905
700 0.3700 1.5492
For the temperature range 300 K to 3200 K: 750 0.3820 1.5994
CP = 0.44391 + (0.30795 10-4)T 800 0.3930 1.6454
(0.61257 105)T-2 + (0.10795 108)T-3 850 0.4020 1.6831
This expression yields calculated values within 1.5 900 0.4090 1.7124
percent of the experimental values for the entire 950 0.4150 1.7375
temperature range. 1000 0.4210 1.7626
Table 15-2 represents the best fit of the values for typi- 1100 0.4320 1.8087
cal manufactured graphite with proper consideration 1200 0.4430 1.8547
given to the accuracy of the individual measurements.
1300 0.4520 1.8924
Sample Calculation: 1400 0.4600 1.9259
Determine the heat capacity of a sample of graphite at 1500 0.4680 1.9594
Btu scanning
500C using a differential cal calorimeter (DSC)
1 =1 1600 0.4740 1.9845
lb F g C the calorimetric
and a strip chart recorder to follow
1800 0.4860 2.0348
response for the temperature scans of 30C. DSC scans
are taken for the sample of graphite, a sapphire refer- 2000 0.4960 2.0766
ence sample and the baseline for correction of the 2200 0.5040 2.1101
measured response. The heat capacity, CP is then 2400 0.5110 2.1394
calculated for the graphite using the formula:
2600 0.5160 2.1604
WS D
CP (graphite) = S CP (sapphire) 2800 0.5210 2.1813
WG DG
3000 0.5270 2.2064
Where: WS = Weight of sapphire
3200 0.5360 2.2441
WG = Weight of graphite
DS = Signal displacement of sapphire 3400 0.5480 2.2944
DG = Signal displacement of graphite 3600 0.5800 2.4283
3800 0.6900 2.8889
0.023 g 40 cal
CP (graphite) = 0.19
0.077 g 52.5 g C
POCO GRAPHITE, INC. PROPERTIES AND CHARACTERISTICS OF GRAPHITE 29
cal J
CP (graphite) = 0.382 = 1.6
g C gK
SPECIFIC HEAT
Btu cal
1 =1
lb F g C
Let the weight of the sapphire reference = 0.203 g and under the same experimental conditions. The DSC
a sample of AXF-5Q graphite, i.e., indicating a density curve rises linearly resulting from the change in heat
W D
CP (graphite)
of 1.82 g/cm = S 1.5S mm
3 and measuring CP(sapphire)
6 mm diameter, capacity of the sample as a function of temperature.
WG DG
weigh 0.077 g, respectively. CP of sapphire is 0.19 cal/ Sapphire is routinely used as a reference material
(gC). CP of graphite at 500C can be calculated by since it is stabilized, i.e., will not oxidize, and due to
knowing the displacement as determined from the the fact that heat capacity for sapphire has been thor-
strip chart recorder. oughly investigated and well documented. Once the
baseline and accuracy have been established, a third
Assume the displacement (corrected) is 40.0 for the
run is made on the sample of interest under the same
graphite and 52.5 for the sapphire reference.
experimental conditions.
Therefore:
There is no standard test method for determining
0.023 g 40 cal specific heat of graphite, but the DSC method is com-
CP (graphite) = 0.19
0.077 g 52.5 g C monly used for specific heat determination of other
cal J materials.
CP (graphite) = 0.382 = 1.6
g C gK Another simple method which yields approximate spe-
cific heat data is an ice calorimeter. If a body of mass
Test Method (m) and temperature (t) melts a mass (mI) of ice, its
temperature being reduced to 0C, the specific heat of
The previous example best illustrates how a DSC and
the substance is:
a chart recorder may be used in determining heat
capacity. However, modern technology has integrated 80.1m
S=
the DSC with computer and software technology, mt
2.5
thereby eliminating the needWfor calculating CP from
S,
a chart recorder. POCO =
En,currently uses a Netzsch STA-
WBB,
449 Heat Flux DSC (Figure 15-1) for evaluating 2.0 AXF-5Q
graphite and other related materials. Heat capacity (Taylor-Groot)
calculations are made via software but the fundamen-
CP (J/g K)
Gas outlet
1.0
Furnace C 1 1
logEn, = Protective
2.303
tube
T TA, 0.5
DSC sensor 0 500 1000 1500 2000 2500 3000
Temperature (C)
Hoisting
device Figure 15-2. Specific heat vs. temperature: POCO graphite
Gas inlet
ple in the sample crucible and taking measurements Graphite. (West Lafayette, Indiana: Purdue University, July 1978.
[NTIS No. ADA060419]), p.15.
1.5
Normal spectral emissivity written as a function of
temperature is:
1.0 Manufactured graphite WS,
American Institute of Physics En, C= 1 1
0.5
Handbook, 3rd edition, 1972
logEn, = WBB,
2.303 T TA,
0.0 POCO AXF-5Q graphite
C 1 1
logEn, =
Where: C = 14,380 micron
2.303 W
K S T T
0 1000 2000 3000 4000 En, = A,
Temperature (C)
= 0.65 micron WBB
T = Temperature of material (K)
Figure 15-3. Specific heat of manufactured graphite TA, = Apparent temperature of material (K)
For a specific temperature the
WStotal normal emissivity
E =
Emissivity can be expressed as:= n,C WBB 1 1
logEn,
2.303 T TA,
W
= T4 S
En, =
Definition En,t WA,t
T4BB
A measure of the heat radiating ability of a surface is Where:
referred to as emissivity. Total emissivity or spectral
WS = Normal total radiant energy emitted by a specimen
emissivity are ways to express it. The total emissivity T4A,t area and unit solid
material per unit Etime, unit
is defined as the ratio of thermal energy emitted by a n,t =
angle. TW4
material per unit time per unit area to that emitted by En, = 4 S
TWA,t
a black body over the entire band of wavelengths when En,t =energy
WBB = Normal total radiant BB emitted by a black
T4 unit area and unit
body reference per unit time,
both are at the same temperature. A black body, i.e.,
ideal radiator, is one which absorbs all the radiant solid angle.
energy falling on it and, at a given temperature, radi- Total normal emissivity at elevated temperatures can
ates the maximum amount of energy possible over the be expressed as:
entire spectrum of wavelengths.
T4A,t
En,t =
The spectral emissivity is defined as the ratio of ther- T4
mal energy emitted by a material per unit time per
unit area to that emitted by a black-body reference Where: T = Temperature of material (K)
where radiation from both are of the same wavelength TA,t = Apparent temperature of material (K)
and both are at the same temperature. The spectral Emissivity data has usefulness in applications such as
emissivity of graphite has been measured at 6500 . aerospace, heaters, pyrometry, etc., but published data
Dull surfaced graphite and polished graphite have is difficult to find.
had typical values of 0.90 and 0.77, respectively. It has
been determined that the emissivity of graphite does Test Method
vary slightly with temperature. A temperature coeffi-
cient of 1.9 10-5/K has been determined. Graphite There are no standard methods for measuring emissiv-
emissivity has been found to be nearly constant in the ity of graphite, but one method used to measure the
wavelength range 2000 to 60,000 . Spectral emissiv- emissivity of graphite is described by Grenis and
ity values approaching 0.99 have been measured for Levitt.13 A schematic of this equipment can be seen
graphite near sublimation temperatures of 3600 K.
13 Grenis, A.F. and Levitt, A.P., The Spectral Emissivity and Total
For a specific temperature, at a specific wavelength,
Normal Emissivity of Graphite at Elevated Temperatures.
normal spectral emissivity can be expressed as: (Watertown, Mass.: Watertown Arsenal Laboratories, November
1959. [NTIS No. ADA951659]), p.14.
in Figure 16-1. The methods of measuring emissivity TABLE 16-1. TOTAL EMITTANCE
are wrought with difficulties and results may be biased Temperature POCO POCO Pyrolytic
due to equipment and/or assumptions made in run- (K) AXM-5Q AXF-5Q Graphite
ning the tests. At best, the testing is at a research 1700 0.833
level and not a routine procedure.
1800 0.787 0.835
Holders and electrodes
Specimen 1900 0.793 0.837
(C)
2000 0.799 0.840
Total
Micro-optical 2100 0.805 0.842
radiation
pyrometer (O)
detector
2200 0.811 0.844
Vacuum/pressure
chamber 2300 0.817 0.846 0.510
2400 0.823 0.849 0.504
Millivolt Precision
temperature potent- 2500 0.829 0.851 0.499
recorder (M) iometer (P)
2600 0.835 0.853 0.493
2700 0.841 0.856 0.487
2800 0.847 0.858 0.481
Power D.C. Vacuum 2900 0.853 0.860 0.476
Micro-optical
and controls pump and pyrometer (O)
(E) gauges (V) 3000 0.470
Figure 14-1. Schematic block diagram of the emissivity apparatus The measured values of the total emittance of the
graphite specimens are shown in Table 16-1 and again
POCO Graphites vs. Conventional Graphites graphically in Figure 16-2.
Very little information on the emissivity of graphite
is available. The following information on total emit- 0.87
tance of two grades of POCO graphite and pyrolytic
graphite has been reported by Cezairliyan and
0.86
Righini.14
The equation for total emittance of POCO (AXM-5Q) AXF-5Q
Total Emittance
0.85
graphite as a function of temperature, between 1800
to 2900 K is:
0.84
E = 0.679 + (6.00 10-5)T AXM-5Q
Where: T is in K.
The differences may be associated with layer plane
orientation or other crystallographic effects, particu-
larly when comparing a pyrolytic graphite to a
polycrystalline graphite such as AXM-5Q. The differ-
ence seen between AXF-5Q and AXM-5Q may go back
to a surface roughness effect, but are primarily associ-
14 Cezairliyan, A. and Righini, F., Measurements of Heat Capacity, ated with the porosity differences with regard to size
Electrical Resistivity, and Hemispherical Total Emittance of Two and frequency distribution across the surface.
Grades of Graphite in the Range of 1500 to 3000K by a Pulse
Heating Technique, Rev. in Htes Temp. et Refract., t.12 (1975),
p. 128.
POCO Graphites vs. Conventional Graphites TABLE 17-2. TYPICAL PURITY ANALYSIS
PURIFIED POCO GRADES
When discussing nonpurified graphites, POCO graph- TOTAL ASH RANGE 5 PPM OR LESS
ites are fairly clean, i.e., contain relatively low levels of
Element Element Detected ppm Range
impurities. However, since graphitization temperature
has a strong bearing on the impurities which remain, Silicon (Si) Yes Trace
the ash levels on any product can vary accordingly. Sulfur (S) Yes Trace
There are other process steps which influence the
Vanadium (V) Yes Trace
final ash level also.
Calcium (Ca) Yes Trace
In material which has been impregnated for densifica-
Boron (B) Yes Trace
tion, contaminants in the raw material used could
increase the impurity content as well. Aluminum (Al) Yes Trace
Magnesium (Mg) Yes Trace
POCO graphites will typically range from 3003000
ppm total impurities, depending on the grade and Iron (Fe) Yes Trace
density. Many conventional graphites fall within this Molybdenum (Mo) Yes Trace
range also, but some will be in the range of 0.1 percent
Phosphorus (P) Yes Trace
(1000 ppm) to several percent (20,00030,000 ppm).
Nickel (Ni) No
Purified POCO graphite will have less than 5 ppm total
Titanium (Ti) No
impurities. This is one of the best grades of purified
graphite available anywhere. The unique nature of the Potassium (K) No
POCO pore structure and relatively clean raw materi- Sodium (Na) No
als aids in allowing this ultra-high purity. Typical Copper (Cu) No
analysis of a purified POCO graphite is seen in Table
17-2. Purified graphites can be produced in several Chromium (Cr) No
ways. Simply heat-treating to very high temperatures, Zinc (Zn) No
usually in excess of 3000C, will volatilize most heavy Lithium (Li) No
elements present. Halogen gases, such as chlorine or
fluorine, will react with the impurities at high temper-
ature and volatilize off as chloride or fluoride salts.
Some elements such as boron are very stable and diffi- Oxidation
cult to remove, especially since they can substitute for
carbon atoms in the crystal structure. Definition
Oxidation is a chemical reaction that results in elec-
Temperature Effects trons being removed from an atom, which makes the
The only real temperature effect on ash levels comes atom more reactive so that it may join with one or
from the graphitization temperature or a subsequent more other atoms to form a compound. When talking
thermal processing to remove impurities. As men- about carbon and graphite, oxidation is normally
tioned previously, the higher the final thermal thought of as the reaction of carbon atoms with
treatment, the lower the ash level will usually be. oxygen to form carbon monoxide (CO) and carbon
dioxide (CO2). However, many other gases (besides
Density Effects oxygen) will react with carbon in an oxidation reac-
tion (e.g., CO2, H2O, N2O, etc.). The result of the
In POCO graphite, a slight trend has been noted oxidation reaction is a loss of carbon atoms from
with ash as related to density. Since POCO graphites the carbon or graphite material, which obviously
have increasingly more open porosity as the density affects many of its properties and characteristics. If
decreases, more opportunity for volatilization escape oxidation of a piece of carbon is allowed to continue
of the impurities during graphitization can occur. long enough, all the carbon atoms will react to form
Consequently, slightly lower ash levels are typically a gas (or gases) which dissipates and leaves behind
found for the lower-density grades. This may be unique nothing except a small amount of ash, which is the
to POCO graphites. The difference is relatively small oxides of the metallic impurities that were present
though, so it is mentioned only in passing, as a number in the carbon to begin with.
of other factors may have more significant effects on
the final ash level.
The oxidation of carbon by oxygen (as well as other POCO Graphites vs. Conventional Graphites
gases) is highly temperature-dependent.
CA 100 No detectable
reaction occurs at temperatures up to about 350C. The oxidation characteristics of any graphite at the
BA
As the temperature is increased, the rate of reaction same temperature and atmospheric conditions are
increases rapidly, according to the well-known dependent on the amount of impurities in the mate-
Arrhenius expression: rial, the density of the material and the amount of
surface area available to react with the oxidizing
In K E/RT atmosphere. POCO graphites can be impregnated with
Where: T = Temperature
a proprietary oxidation inhibitor that can substantially
E = Activation energy increase its oxidation resistance. Purification also
K = Reaction rate reduces oxidation significantly by removing metallic
R = Universal gas constant impurities, which act as oxidation catalysts.
As the surface area increases, the oxidation rate
%WTL = WTOWTF 100 = 10.00009.9900 100 = 0.1%
Test Method
WTO 10.0000 increases, too. This is expected, as the surface
To measure the oxidation characteristics of a particular exposure is important to the oxidation process. For
carbon material, a piece of known weight is exposed to purposes of standardization and to minimize the effect
the oxidizing environment of interest for some period of variable surface area to volume (SA/V) ratios, the
Ashand
(ppm) = C A 1,000,000 = use of a sample with an SA/V ratio of 10:1 is used at
of time, then reweighed, to determine a weight
B weight
loss (the oxidation A loss). There is not a widely Entegris for testing oxidation rates.
accepted standard
35.0004 test for measuring
35.000 the oxidation
0.9P2) = 5 1 ppm
Eo (1 1.9P +1,000,000 Temperature Effects
characteristics of carbon
115.0000 materials
35.000 (TDI 4.1.1.7 and
4.1.1.8 in Appendix B). The differences in oxidation behavior of the various
The oxidation characteristics of carbon are usually grades of graphite are widest at the lowest tempera-
expressed in one of two different ways: tures, tending to disappear as the temperature
increases. The oxidation threshold temperature,
1. The percent weight loss in 24 hours at a given tem- defined as that at which a sample loses approximately
perature, often referred to as oxidation resistance one percent of its weight in 24 hours, is about 570C
CA 100
2. The temperature at which for purified graphite, while nonpurified graphite is
BA a sample loses approxi-
mately one percent of its weight in a 24-hour period, about 430C (Figure 18-1).
which is called the oxidation threshold temperature The oxidation of graphite is highly temperature-
of the material being tested dependent. At temperatures up to about 350C, no
In K E/RT detectable oxidation occurs. As the temperature is
Sample Calculation: increased, the rate of reaction increases rapidly,
If a sample originally weighed 10.0000 grams after according to the Arrhenius equation (Figure 18-2).
being dried and 9.9900 grams after oxidation testing,
the percent weight loss would be 0.1 percent. Density Effects
Since the oxidation of graphite is a surface reaction,
%WTL = WTOWTF 100 = 10.00009.9900 100 = 0.1% it is known that the rate of oxidation is affected by
WTO 10.0000
the porosity of the material. As the percent porosity
increases, the apparent density of the material will
Where: WTO = Initial sample weight (dried)
decrease. Therefore, as the apparent density decreases,
WTF = Sample weight after oxidation testing percent
the rate of oxidation will increase. However, the
WTL = Percent weight loss
effects of impurities and their catalytic action can
easily override the density effects. Purified data shows
Eo (1 1.9P + 0.9P2) the density difference more clearly, but it is, neverthe-
less, relatively small when other factors are
considered.
100 10
% Weight Loss/24 hours
% Weight Loss/hour
10 1
1 Threshold 0.1
0.1 0.01
0.01 0.001
300 400 500 600 700 800 900 1000 300 400 500 600 700 800 900 1000
Temperature (C) Temperature (C)
100 10
% Weight Loss/24 hours
% Weight Loss/hour
10 1
1 0.1
Threshold
0.1 0.01
0.01 0.001
300 400 500 600 700 800 900 1000 300 400 500 600 700 800 900 1000
Temperature (C) Temperature (C)
Figure 18-1. Oxidation threshold Figure 18-2. Oxidation rate
Serlie, M. and Oye, H.A., Cathodes in Aluminium Washburn, E.W., Phys. Rev., 17, 273 (1921).
Electrolysis, 2nd Edition, Dusseldorf, Germany,
Wirt, W., Specific Heat of POCO Graphite AXF-5Q at
Aluminium-Verlag (1994).
Several Temperatures Between 30500C, Job No.
Spain, I.L., Electronic Transport Properties of 84-826 Prepared for Maxwell Laboratories, Analytical
Graphite, Carbons, and Related Materials, Chemistry Service Center, September 18, 1984.
and Physics of Carbon, 16 (1981), p. 119.
Xue, J.S. and Dahn, J.R., Dramatic Effect of Oxidation
Taylor, R.E. and Groot, H., Thermophysical Properties on Lithium Insertion in Carbons Made from Epoxy
of POCO Graphite. (West Lafayette, Indiana: Purdue Resins, J. Electrochem. Soc., 142, 36683677 (1995).
University, July 1978. [NTIS No. ADA060419]).
Zhao, J., Wood, J.L., Bradt, A.C. and Walker, P.L., Jr.,
Walker, P.L., Jr., Chemistry and Physics of Carbon, Oxidation Effects on CTE and Thermal Shock
New York: Marcel Dekker, Inc., Vols.17, 19651971. Fracture Initiation in Polycrystalline Graphites,
Carbon, 19 No. 6, (1981), 405408.
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Physics of Carbon, New York: Marcel Dekker, Inc.,
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