Designation: D6558 − 00a (Reapproved 2010)

Standard Test Method for

Determination of TGA CO2 Reactivity of Baked Carbon
Anodes and Cathode Blocks1
This standard is issued under the fixed designation D6558; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. A
superscript epsilon (´) indicates an editorial change since the last revision or reapproval.

1. Scope 3.1.1 dusting, n—that quantity of carbon that falls off the
1.1 This test method covers the thermogravimetric (TGA) carbon artifact while in the reaction chamber and is collected in
determination of CO2 reactivity and dusting of shaped carbon the container at the bottom of the reaction chamber.
anodes and cathode blocks used in the aluminum reduction 3.1.2 final CO2 reactivity, n—the mass loss of the carbon
industry. The apparatus selection covers a significant variety of artifact during the final 30 min of exposure to CO2 in the
types with various thermal conditions, sample size capability, reaction chamber divided by the initial geometric (right cylin-
materials of construction, and procedures for determining the drical) exposed surface area of the sample, expressed as
mass loss and subsequent rate of reaction. This test method mg/cm2-h.
standardizes the variables of sample dimensions, reaction 3.1.3 initial CO2 reactivity, n—the mass loss of the carbon
temperature, gas velocity over the exposed surfaces, and artifact during the first 30 min of exposure to CO2 in the
reaction time such that results obtained on different apparatuses reaction chamber divided by the initial geometric (right cylin-
are correlatable. drical) exposed surface area of the sample, expressed as
1.2 The values stated in SI units are to be regarded as mg/cm2-h.
standard. No other units of measurement are included in this 3.1.4 total CO2 reactivity, n—the total mass loss of the
standard. carbon artifact (including dusting) during the total time that the
1.3 This standard does not purport to address all of the sample is exposed to CO2 (420 min) in the reaction chamber
safety concerns, if any, associated with its use. It is the divided by the initial geometric (right cylindrical) exposed
responsibility of the user of this standard to establish appro- surface area of the sample, expressed as mg/cm2 -h.
priate safety and health practices and determine the applica-
4. Summary of Test Method
bility of regulatory limitations prior to use.
4.1 Initial, final, and total CO2 reactivity and dusting are
2. Referenced Documents determined by passing carbon dioxide gas at flow rates giving
2.1 ASTM Standards:2 a standard velocity of reactant gas around cylindrically shaped
D6353 Guide for Sampling Plan and Core Sampling for carbon artifacts under isothermal conditions for a specified
Prebaked Anodes Used in Aluminum Production length of time. The reactivity is determined by continuously
D6354 Guide for Sampling Plan and Core Sampling of monitoring the sample mass loss. The dusting term is deter-
Carbon Cathode Blocks Used in Aluminum Production mined by collecting and determining the mass of carbon
E691 Practice for Conducting an Interlaboratory Study to particles that fall off the sample during reaction.
Determine the Precision of a Test Method
5. Significance and Use
3. Terminology 5.1 The CO2 reactivity rates are used to quantify the
3.1 Definitions of Terms Specific to This Standard: tendency of a carbon artifact to react with carbon dioxide.
Carbon consumed by these unwanted side reactions is unavail-
able for the primary reactions of reducing alumina to the
1
This test method is under the jurisdiction of ASTM Committee D02 on primary metal. CO2 dusting rates are used to quantify the
Petroleum Products and Lubricantsand is the direct responsibility of Subcommittee tendency of the coke aggregate or binder coke of a carbon
D02.05 on Properties of Fuels, Petroleum Coke and Carbon Material.
Current edition approved May 1, 2010. Published June 2010. Originally artifact to selectively react with these gases. Preferential attack
approved in 2000. Last previous edition approved in 2005 as D6558–00a (2005). of the binder coke or coke aggregate of a carbon artifact by
DOI: 10.1520/D6558-00AR10.
2
these gases causes some carbon to fall off or dust, making the
For referenced ASTM standards, visit the ASTM website, [Link], or
carbon unavailable for the primary reaction of reducing alu-
contact ASTM Customer Service at service@[Link]. For Annual Book of ASTM
Standards volume information, refer to the standard’s Document Summary page on mina and, more importantly, reducing the efficiency of the
the ASTM website. aluminum reduction cell.

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 D6558 − 00a (2010)
5.2 Comparison of CO2 reactivity and dusting rates is useful within 5 mm of the center. The furnace shall be large enough
in selecting raw materials for the manufacture of commercial to accept the reaction chamber.
anodes for specific smelting technologies in the aluminum [Link] Reaction Chamber, consisting of a vertical tube
reduction industry. constructed of a material capable of withstanding the tempera-
5.3 CO2 reactivity rates are used for evaluating effective- ture of the reaction (960 6 2°C) with sufficient inside diameter
ness and beneficiation processes or for research purposes. (ID) to accept the sample and sample holder while not affecting
the gas flow to and from the sample (100 6 25-mm ID is
6. Apparatus recommended). The reaction chamber is to be constructed with
6.1 The apparatus to be used should be as simple as possible a dust collection cup at the bottom that is removable and
and be commensurate with what is to be achieved, the principal capable of capturing all the dust that falls off the sample during
criteria being that the reaction rate is to be determined under the test. The most common materials of construction are quartz
isothermal conditions and unaffected by physical and chemical and Inconel.
properties inherent to the apparatus (such as gas diffusion [Link] Sample Holders, capable of supporting the sample in
patterns, gas temperature, exposed sample surface area, and so the reaction chamber for the duration of the test and should be
forth). A typical apparatus that has been found to be suitable is capable of being reusable. The sample holder shall not change
illustrated in Fig. 1. in mass during the test, affect the diffusion pattern of the gases
6.1.1 Furnace and Controller, capable of maintaining con- to or from the sample, limit the gas accessible surface area of
stant temperature, within 62°C in the 100-mm region centered
the test sample, or interfere with the free fall of dust from the
on the specimen. The example apparatus of Fig. 1 employs a
sample. A typical sample holder is illustrated in Fig. 2.
three zone heating element and associated controls to accom-
plish this, but other methods such as tapered windings or long [Link] Gas Preheat Tube, extending into the first heat zone
linear heaters are also suitable. The control thermocouple is a of the reaction chamber to preheat the gases prior to entering
grounded type and shall be located within the reaction chamber the reaction chamber. The length and diameter of the tube can
near the surface of the test sample to allow the furnace vary as long as the gases exiting the tube are the same
controller to adjust to exothermic reactions, which occur temperature as the reaction chamber. The inlet gas shall exit the
during air reactivity tests, if the furnace is also used for air preheat tube downward to prevent channeling of the gas
reactivity testing. The control thermocouple shall be positioned through the reaction chamber and to prevent plugging of the
4 6 1 mm from the side sample surface and centered vertically preheat tube with carbon dust.

FIG. 1 Typical CO2 Reactivity Apparatus

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 D6558 − 00a (2010)
8. Sampling
8.1 Shape the carbon specimen by coring and cutting or
machining to a right cylindrical geometry, 50 6 1.0 mm in
length and 50 6 1.0 mm in diameter. Most sample holders
require a hole of about 3-mm diameter to be drilled vertically
through the center of the cylinder to accommodate a hanger.
The shaped specimen is to be smooth and free of visible cracks
and gouges. Sampling plans for anodes and cathode blocks
given in Guides D6353 and D6354 may be used if desired.
8.2 Dry the shaped specimen in an oven at 105 6 5°C to
constant weight.
8.3 Make the sample free of loose carbon dust and impuri-
ties from the shaping process by blowing with dry air.

9. Calibration
9.1 The purpose of this procedure is to establish a relation-
ship between the controller settings for three zone furnaces and
the actual temperatures inside the reaction chamber in the
region of the specimen. The length to be calibrated is a
100-mm (4-in.) zone.
NOTE 1—For single zone furnaces, the calibration probe shall be placed
FIG. 2 Typical Sample Holder in center of where sample will be placed and confirm that the 100-mm
zone is within 62°C.
9.1.1 Insert a multiprobe thermocouple (for example, three
[Link] Balance, capable of measuring the weight of the couples in same sheath with probes located at the tip, and at 50
sample and sample holder (approximately 200 g maximum) and 100-mm (2 and 4 in.) above the tip; or a packet of
continuously throughout the duration of the test to the nearest thermocouples with tips located at similar known distances)
0.01 g. into the zone where the sample will be located. The multiprobe
[Link] Gas Flow Meter, capable of monitoring the gas flow thermocouple center probe shall be located where the center of
rate into the reaction chamber. All gas flow rates are to be the sample will be located.
maintained at the rate determined for the particular test
9.1.2 The center thermocouple is connected to the main
apparatus.
controller setting, that is, 960°C for CO2 reactivity.
[Link] Needle Valve, to make fine adjustments to the gas
9.1.3 Connect the other two (2) thermocouples to any
flow rate.
temperature indicating device. For determining actual tempera-
[Link] Pressure Reducing Valve, to reduce the pressure of
ture profile, a recording temperature indicator is required.
the compressed gases to near atmospheric pressure prior to
entering the gas flow meter through the needle valve. 9.1.4 Allow 4 h for furnace to reach equilibrium under
[Link] Thermocouple(s), inserted into the reaction chamber nitrogen purge (rate per 9.2).
to calibrate the furnace zone controllers. An optional thermo- 9.1.5 Adjust zones until all three (3) temperature indicators
couple may be used to monitor reaction temperatures. Some are 62°C.
users find continuous temperature measurement of the internal 9.2 Gas Flow Rates, for this test are based on 250 6 5 L/h
reaction chamber to be of value. (ambient temperature) for a sample diameter of 50 mm and a
[Link] Calipers, or other suitable device, capable of mea- reaction tube with an ID of 100 mm. Reactivities determined
suring to within 0.01 mm for determining the sample diameter with this test method are affected by the gas velocity sweeping
and height to calculate geometric surface area exposed to the the reaction surfaces during the test. This requires gas flow
test gases. rates to be such that the velocity through the annular space
[Link] Optional Equipment, including, but not limited to, between the sample and reaction tube wall is constant for
automatic control devices, multichannel line selector, and various size reaction tubes. The proper flow rate for other
personal computer to automate data gathering, manipulation, geometries is determined by multiplying the reference flow rate
reporting, and storage. (250 L/h) by the ratio of annular area of the system to the
annular area of the reference system. For example, a 75-mm ID
7. Reagents tube with 50.8-mm samples would have a flow rate calculated
7.1 Purity of Reagents—Reagent grade, conforming to the by:
specifications of the Committee on Analytical Reagents of the Ratio5 (1)
American Chemical Society.
7.1.1 Nitrogen—99.95 %.
7.1.2 Carbon Dioxide—99.95 %. F Tube ID2 2 Sample OD2
2
Ref Tube ID 2 Ref Sample OD 2 5 G F
752 2 50.82
1002 2 502
5
3044
7500 G
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 D6558 − 00a (2010)
5 0.406 where:
TRc = total CO2 reactivity rate, mg/cm2-h,
Flow Rate 5 @ 250 L/h # · @ 0.406# 5 102 L/h (2) Wi = initial sample weight, g, and
Wf = final sample weight, g.
10. Procedure
11.3 Calculate initial CO2 reactivity rate (IRc) as follows:
10.1 Preheat the reactor tube to 960 6 2°C for CO2
2000~ W i 2 W 30!
reactivity. IRc 5 (6)
A
10.2 Purge the reaction chamber with nitrogen at the flow
rate determined in 9.2. where:
IRc = initial CO2 reactivity rate, mg/cm2-h, and
10.3 Weigh and record the mass of the sample to the nearest W 30 = sample weight after 30 min of test, g.
0.01 g as Wi.
11.4 Calculate final CO2 reactivity rate (FRc) as follows:
10.4 Measure the sample diameter ( ds), sample height (h),
and diameter of the center hole (dh) to 60.01 mm to calculate 2000~ W 390 2 W f !
FRc 5 (7)
geometric surface area for the reaction as given in 11.1. A

10.5 Insert the sample into the reaction chamber by placing where:
the sample in the sample holder and suspending the sample FRc = final CO2 reactivity rate, mg/cm2-h, and
holder from the balance. W 390 = sample weight after 390 min of test, g.
10.6 Preheat the sample under nitrogen purge for 30 min. 11.5 Calculate CO2 dusting rate (DRc) as follows:
10.7 Tare the balance in accordance with the balance 1000W d
DRc 5 (8)
manufacturer’s instructions. 7A
10.8 Switch the gas introduced to the reaction chamber from where:
nitrogen to CO2 after 30 min in the nitrogen preheat, and DRc = dusting rate during 7 h test, mg/cm2-h, and
maintain the flow rate as determined in 9.2. Wd = weight of dust collected during test, g.
10.9 Record the weight of the sample every minute for the
12. Report
duration of the test. The test duration for CO2 reactivity is 7 h
(420 min). 12.1 Report reactivity results to the nearest 0.1 mg/cm2-h.
10.10 Remove the sample from the reaction chamber as 13. Precision and Bias3
soon as possible after the test time has expired as the dusting
13.1 Precision—The precision was determined by an inter-
parameter will be affected. Exercise care so that the sample
laboratory study conducted in accordance with Practice E691.
does not strike the sides of the reaction chamber upon removal,
Six laboratories tested nine materials (seven anodes and two
which could result in dislodging particles and adding to the
cathodes). It was found, by linear regression, that the repeat-
mass of dust.
ability and reproducibility are dependent on the average value
10.11 Remove the dust collection cup from the bottom of of the measured rate. Consequently, the regression equation is
the reaction chamber and place in a desiccator until cool. used in the precision statements. Based on this study, the
10.12 Weigh the dust collected in the dust collection cup, criteria in 13.1.1 and 13.1.2 shall be used for judging the
and record as Wd. acceptability of results (95 % probability):
13.1.1 Repeatability Limits—Duplicate values (mg/cm2-h)
11. Calculation by the same operator using the same equipment shall not be
considered suspect unless the determined values differ by more
11.1 Calculate the exposed surface area of the shaped
than the r value given by the following equations:
sample as follows:
[Link] Total CO2 Rate: r = (0.4977 × x) + 3.1512 x =
A 5 Area of (3) average of duplicate total CO2 rate values [Applicable between
11 and 42 mg/cm2-h total CO2 rate]
$ circumference1top and bottom ~ surfaces 2 center hole! % , or
[Link] Initial CO2 Rate: r = (–0.1804× x) + 6.9468 x =
H
A 5 pd s h1
2p 2
4 J
~ d s 2 d 2h ! /100 (4) average of duplicate initial CO2 rate values [Applicable be-
tween 5 and 17 mg/cm2-h initial CO2 rate]
where: [Link] Final CO2 Rate: r = (0.4918 × x) – 1.5454 x =
average of duplicate final CO2 rate values [Applicable between
A = exposed surface area, cm2,
ds = sample diameter, mm, 14 and 57 mg/cm2-h final CO2 rate]
dh = diameter of central hole (if any), mm, and [Link] CO2 Dusting Rate: r = (0.919× x) + 0.4796 x =
h = sample height, mm. average of duplicate CO2 dusting rate values [Applicable
between 0.3 and 5 mg/cm2-h CO2 dusting rate]
11.2 Calculate total CO2 reactivity rate (TRc) as follows:
1000~ W i 2 W f ! 3
Supporting data have been filed at ASTM International Headquarters and may
TRc 5 (5)
7A be obtained by requesting Research Report RR:D02-1494.

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 D6558 − 00a (2010)
13.1.2 Reproducibility Limits—The values (mg/cm2-h) re- [Link] Final CO2 Rate: R = (0.8985 × x) – 5.6199 x =
ported by each of two laboratories, representing the arithmetic average of duplicate final CO2 rate values [Applicable between
average of duplicate determinations, shall not be considered 14 and 57 mg/cm2-h final CO2 rate]
suspect unless the reported values differ by more than the R [Link] CO2 Dusting Rate: R = (2.2671× x) + 0.8844 x =
value given by the following equations: average of duplicate CO2 dusting rate values [Applicable
[Link] Total CO2 Rate: R = (1.0706 × x) – 9.2078 x = between 0.3 and 5 mg/cm2-h CO2 dusting rate]
average of duplicate total CO2 rate values [Applicable between 13.2 Bias—This test method has no bias because the values
11 and 42 mg/cm2-h total CO2 rate] of CO2 reactivity are defined in terms of this test method.
[Link] Initial CO2 Rate: R = (–0.1101× x) + 9.9455 x =
average of duplicate initial CO2 rate values [Applicable be- 14. Keywords
tween 5 and 17 mg/cm2-h initial CO2 rate] 14.1 anode; cathode block; CO2 reactivity; dusting

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