IMPROVED STANDARDS FOR IODINE ADSORPTION NUMBER
NUJoyce
MB E R
By George
(COLUMBIAN CHEMICALS COMPANY, MARIETTA, GA)
INTRODUCTION
During the ASTM International D24 Meetings in 2001 Columbian Chemicals Company (CCC) presented
information indicating that carbon blacks, specifically some of the standard reference tread blacks, have not
exhibited a stable iodine adsorption number. Laboratory testing with tread SRB’s indicated their iodine numbers
dropped continuously over time, and such an observation casts doubt as to the validity of using such materials as
references or standards with assigned target values. Because of the importance of iodine adsorption testing within
the carbon black industry and the need for carbon black iodine number standards, a Task Force was formed to
address this issue.
In June 2002 a D24 research report was presented entitled “Improved Standards for Carbon Black-Iodine
Adsorption Number”. This report documents not only the problem of iodine number instability with tread blacks
but also the reason for the problem, and most importantly a solution to improving the standards. This research
report describes the manufacture of two new experimental standards, HT-B6 and HT-E6, designed to provide a
stable iodine number for use as an improved standard. HT-B6 and HT-E6 are partially graphitized carbon blacks
prepared from the SRB’s B-6 and E-6.
Initial round robin testing of the new experimental standards was completed in December 2002. This study
included data from 36 laboratories world-wide providing target values for the new experimental standards along
with updated values for the SRB’s B-6 and E-6. The target values for these new HT standards along with B-6 and
E-6 are also located on ASTM International’s website at www.astm.org.
IODINE NUMBER INSTABILITY
The recent revision to ASTM D4821 contains both discussion and actual laboratory test data describing the
potential problems typically associated with iodine number testing. These are found in sections 6.1.1 and Figures 1
and 3 of the standard. Figure 1, also shown below, is a short-term x-chart of the SRB B-5 (N330) showing a target
or mean value of 77.7 mg/g. The original published target value for SRB B-5 was 79.1 mg/g. Both target values for
B-5 were obtained through ASTM round robin studies based on short-term testing within multiple laboratories, but
were obtained at different points in time. The original study led to the target value of 79.1 mg/g, and a few years
later a second study resulted in a target value of 77.7 mg/g. ASTM D4821 Figure 3 is an x-chart of the SRB B-5
iodine adsorption number within a single laboratory, and exhibits a continuous drop in iodine number over a three
year period. This trend chart is shown below in Figure 2.
3 Year Iodine Adsorption X-Chart of B-5
80
79.5
79
Iodine No, mg/g
78.5
78
77.5
77
76.5
76
75.5
75
Figures 1 and 2 (right): SRB B-5 x-charts
Another example of iodine number instability was demonstrated with the SRB B-6. The original published
iodine number target value for SRB B-6 (N220) was 117.9 mg/g. This material was reevaluated for iodine number
after 14 months by several companies and the results are shown in Table 1. The average difference in iodine
number observed during this time was -1.4 mg/g. Because the 3-sigma x-chart limits for this material were
originally calculated to be ± 2.28 mg/g, a change of -1.4 mg/g could easily result in laboratories wrongfully testing
outside recommended x-chart limits.
Table 1: SRB B-6 Iodine Number Change in 14 Months
Company
# Labs
Avg Iodine No
Avg Iodine No
on Nov 2000
on Jan 2002
CCC
1
119.3
117.4
 Iodine No
(14 months)
-1.9
Cooper Tire
1
117.9
115.4
-2.5
Degussa
1
118.4
117.3
-1.1
Cabot
1
118.6
117.6
-1.0
Continental
3
116.4
115.2
-1.2
Sid Richardson
4
116.3
115.6
-0.8
Summary
11
Avg = -1.4
With these well documented cases of iodine number instability, a need for improved materials for use as standards
was identified. The ideal material would preferably be a tread carbon black and exhibit a stable iodine number over
time.
IODINE NUMBER STABILITY
Based on well documented research on modified carbon black samples produced by Columbian Chemicals
Company (CCC) in the early 1990’s1, CCC proposed the use of heat treated or partially graphitized carbon blacks as
candidate material for improved iodine standards. CCC originally produced a series of N121 samples using an
induction furnace to heat treat the carbon black at temperatures of 1000-1500°C under an inert atmosphere. These
modified carbon blacks were thoroughly characterized for analytical and colloidal properties at the time of
manufacture. This original information formed the basis for a 12 year study of iodine stability. The original
analytical data for these samples are shown in Table 2.
Table 2: Original Analytical Properties of Heat Treated N121 Samples
Sample
Iodine
NSA
micropore
Lc
Hydrogen
Oxygen
(mg/g)
(m2/g)
(m2/g)
(nm)
(ppm)
(%)
N121 Control
120.5
128
8
1.46
3046
1.69
N121 HT 1000°C
145.4
138
16
1.49
2820
0.69
N121 HT 1100°C
150.6
135
12
1.55
1965
0.47
N121 HT 1500°C
154.0
130
0
2.71
106
0.18
Both oxygen and hydrogen were measured by Leco using combustion analyzers. Micropore area was determined by difference of NSA
and CTAB adsorption.
These samples were characterized again in 2002 to observe the stability of specific properties including iodine
number, oxygen and hydrogen content. These results are shown in Tables 2 and 3 and Figures 3 and 4.
1
J. A. Ayala, W. M. Hess, A. O Dotson and G. A Joyce,
Rubber Chem & Tech, Vol. 63, No. 5, Nov 1990
Table 3. Iodine Number Stability of HT N121 Samples
Sample
Iodine No.
Iodine No.
Iodine No.
(mg/g)
(mg/g)
(mg/g)
1988
1990
2002
N121 Control*
123.0
120.5
116.8
N121 HT 1000°C
145.4
136.9
N121 HT 1100°C
150.6
143.7
N121 HT 1500°C
154.0
153.9
* Manufactured in 1988. All samples were tested using 1.0g CB per 50mL iodine solution.
Figure 2. Change in Iodine Number of N121 and HT N121 from date of manufacture.
Table 4. Hydrogen and Oxygen Analysis of HT N121 Samples
Sample
Hydrogen
Oxygen
Hydrogen
Oxygen
(ppm)
(%)
(ppm)
(%)
1990
1990
2002
2002
N121 Control
3046
1.69
3195
2.84
N121 HT 1000°C
2820
0.69
3176
1.98
N121 HT 1100°C
1965
0.47
2403
1.27
N121 HT 1500°C
106
0.18
179
0.13
Oxygen and Hydrogen measurements by Leco
Figure 3. Change in oxygen content of HT N121 Samples over 12 years
The data shown in Table 3 and Figure 2 indicate the N121 sample heat treated at 1500°C exhibits
a stable iodine number during the 12 year period, within experimental error, while the N121 control
changed -6.2 mg/g since manufacture. The iodine number instability observed with the N121 control and
the samples heat treated at 1000 and 1100°C appears to be related to the increase in chemisorbed oxygen.
For those skilled in the art, it is common knowledge that an increase in oxygen content of a carbon black
due to oxidation will result in a reduced iodine number.
Likewise, reducing the oxygen content of a
carbon black by such means as devolatilization will result in an increased iodine number. Thus, the
observed decrease in iodine number during the twelve year study for the N121 and N121 samples heat
treated at 1000 and 1100°C is consistent with observed increases in oxygen content.
A few other observations concerning iodine number of these samples are worth noting. First, the iodine
number of the heat treated samples appears to increase with heat treatment temperature from 120.5 for the
control to 154.0 for the HT 1500°C. This effect is related to the decreasing levels of oxygen on the carbon
black. Another observation with these samples is the rate of change in iodine number for the N121 control
was greatest within the first several years as indicated in Figure 2. Finally, the iodine number stability of
the N121 HT 1500°C appears to be related to the fact that the oxygen content of this material did not
change during the 12 year study, within experimental error. It should be noted that these samples were
stored at ambient conditions in a warehouse without temperature control or special packaging. The stable
oxygen content exhibited by the N121 HT 1500°C is believed to be the result of the observed change in
micro-structure as measured by x-ray diffraction (Lc). Based on these observations, a temperature of
1500°C appears to be the minimum temperature needed to impart a change in micro-structure that will
render the carbon black surface resistant to oxygen chemisorption.
HT-B6 and HT-E6
In January 2002 the D24.21 Iodine Number Task Force led by G. Joyce (Columbian Chemicals Company)
and J. Wilson (Cabot Corp.) recommended the preparation of two heat treated carbon blacks, SRB B-6
(N220) and E-6 (N660). These materials were to be prepared in an induction furnace at 1500°C under an
inert atmosphere precisely as the materials produced by Columbian in 1990. In April 2002, 50 lb. of HTB6 and 100 lb. of HT-E6 were prepared by a US commercial carbon company. These experimental
standards were initially forwarded to Columbian Chemicals Company for preliminary analysis.
The initial analysis of the experimental HT-B6 and HT-E6 materials included oxygen content and iodine
number. The results shown in Table 5 indicate the oxygen content of the heat treated carbons was 0.090.10 percent. The SRB B-6 oxygen content was 1.32 percent, and E-6 was 0.60 percent. Based on this
elemental analysis, the heat treatment removed most of the chemisorbed oxygen to levels slightly less than
observed with the N121 HT 1500°C. Based on this elemental analysis, these two experimental standards
exhibit a characteristic of partially graphitized carbon black.
Table 5. Oxygen analysis of HT-B6 and HT-E6 and controls
Material
Furnace
Oxygen
Run
Content
(%)
B-6
1.32
B-6 HT 1500°C
48
0.09
E-6
0.60
E-6 HT 1500°C
40
0.10
E-6 HT 1500°C
49
0.09
The next characterization of these experimental materials was to observe the level and uniformity of
iodine number within each furnace run. Each of the three 50 lb. heat treatments were sampled for five
aliquots then analyzed using 1.0g CB/50 cm3 iodine solution. The results shown in Table 6 indicate a mean
value of 134 mg/g for the HT-B6 and 47.0 - 47.3 mg/g for the two runs of HT-E6. These values represent
increases in iodine number of approximately 12-16 units based on the original target values of the SRB’s
B-6 and E-6 as indicated in Table 7.
Table 6. Iodine number uniformity of the
Test
B-6
E-6
HT 1500°C
HT 1500°C
Run 48
Run 40
1
134.0
47.2
E-6
HT 1500°C
Run 49
47.5
2
134.1
46.8
47.2
3
134.1
47.5
46.9
4
133.8
46.7
47.8
5
133.8
46.8
47.2
Mean
134.0
47.0
47.3
Std Dev
0.15
0.34
0.34
Table 7. Change in iodine number from original SRB target values
Standard
Run
Original
Iodine

Target
No. *
(mg/g)
(mg/g)
B-6
B-6 HT 1500°C
117.9
48
E-6
---
134.0
16.1
35.3
E-6 HT 1500°C
40
---
47.0
11.7
E-6 HT 1500°C
49
---
47.3
12.0
Another issue discussed at this time concerning iodine number testing was related to the physical form of
the sample prior to testing. Information was presented to ASTM D24.21 that indicated the size of the
pellets used for the iodine test appeared to influence the absolute value and precision. Specifically, small
bead sizes appear to result in higher iodine number than large beads. Therefore, this issue of physical form
was addressed prior to distribution of the two experimental standards.
Preliminary Precision Study to Determine the Physical Form of the Experimental
HT Standards (Beads or Powder)
A multi-lab precision study was designed to look at short-term precision of both beads and milled powder
using the HT-B6 material. A second part of the study included a longer testing period within one lab to
increase the number of observations (n) with both beads and powder. Forty eight aliquots of both beads
and powder were distributed among 21 laboratories for a total of 96 samples. Each lab was asked to test
both beads and powder in duplicate for two days using 0.5g CB/25 cm3 iodine (or 1.0g CB/50 cm3 iodine).
A single lab analyzed both beads and powder in duplicate for 6 days. The results of the multi-lab study are
shown in Table 8 and Figures 4 and 5.
Table 8. Precision of physical form study
Material
Multi-lab
Single lab
Mean
Mean
n=4
n=12
Beads
133.8
133.7
Powder
134.2
134.6
Multi-lab
Std Dev
n=4
0.32
Single lab
Std Dev
n=12
0.32
0.26
0.40
Figure 4. HT-B6 iodine number study of physical form. Results indicate poor between-lab
precision (R) for iodine number.
The data shown in Figures 4 and 5 represent each lab’s iodine number for HT-B6, both beads and powder.
The box plots in Figure 4 include both beads and powder. Figure 5 is presented as trend charts, one for
beads and powder. The striking observation from this data is the very poor between-lab reproducibility
observed, while data within labs tends to be very tight. This observation demonstrates very well the
problem with iodine number testing within the carbon black industry today.
Figure 5. HT-B6 iodine number study of physical form.
display in the trend charts.
Each lab’s mean iodine number is
Conclusions from this study were largely based on the data presented in Table 8. These experiments
indicate that test precision (standard deviation) for beads and powder were not sufficiently different to
justify altering the physical form of the beads. In fact, the single-lab data (that has much higher degrees of
freedom) indicates the beads exhibit slightly less variation than powder. Based on a one-way analysis of
variance (ANOVA) of the multi-lab study, the difference in mean level for beads and powder was not
statistically significant at a 95 percent confidence level, though the powder exhibited a slightly higher mean
than beads. Based on these observations the data indicates there is no justification to alter the physical
form of the experimental standards, and the two materials were subsequently distributed in their pelleted
form.
Initial Target Values for HT-B6 and HT-E6
Thirty-six laboratories participated in an ASTM International D24.21 Task Force Study to ascertain target
values for the HT-B6 and HT-E6 standards and also obtain updated target values for SRB B-6 and E-6.
Each lab was asked to test HT-B6 using 0.25g per 25 cm3 iodine solution and the HT-E6 with 0.5g per 25
cm3 iodine, in accordance with D1510. The resulting data was treated per D4483 for outliers and
calculation of precision statistics. The precision data is presented in Table 9. The control chart target
values and limits are presented in Table 10. This information is also posted to the ASTM website at
www.astm.org.
Table 9. Precision data for HT standards and updates for SRB’s
Standard
Mean
Sr
(r)
SR
B-6
117.1
0.39
0.94
1.63
HT-B6
135.6
0.43
0.89
1.04
E-6
35.4
0.39
3.12
0.59
HT-E6
46.0
0.35
2.13
0.51
(R)
3.93
2.18
4.70
3.16
Table 10. Control chart limits for HT standards and updates for SRB’s
Standard
Target
3s
LCL
UCL
B-6
117.1
1.17
115.9
118.3
HT-B6
135.6
1.28
134.3
136.9
E-6
35.4
1.17
34.2
36.6
HT-E6
46.0
1.04
45.0
47.0
The target iodine number for HT-B6 was observed to be 135.6 mg/g, and HT-E6 was 46.0 mg/g.
These values represent significant increases compared to the original untreated carbon blacks, and as
discussed above, is related to the removal of most of the chemisorbed oxygen from the carbon black
surface. The precision data observed within this study indicates, as anticipated, a significant improvement
in between-lab precision (R) for both experimental standards as compared to the SRB’s B-6 and E-6. The
major contributor to this improvement in between-lab precision is the uniformity or consistency of the heat
treated experimental standards.
The current iodine number observed for the SRB B-6 as compared to the original published value
represents a change of - 0.8 units. The current mean value is 117.1 compared to the original value of 117.9
mg/g. This change or decrease in iodine number is directionally consistent with changes observed with
other tread blacks. In general, the decrease in iodine number for carbon blacks appears to be time
dependent, and is very dependent on the total surface area. The effect of surface area is demonstrated
within this sample set. The current iodine number of the SRB B-6 was 35.4 mg/g compared to the original
published target of 35.3 mg/g. This difference of +0.1 mg/g is statistically insignificant, and no change is
observed in the iodine number of the E-6 standard. In conclusion, only the tread grades have exhibited the
instability with iodine testing, and the HT-B6 represents the first material produced to address this problem
for the carbon black industry.
SUMMARY
The problem of iodine number instability with tread blacks has been demonstrated using carbon
blacks manufactured by industry leading producers, and also using ASTM International Testing Standards
that are recognized world-wide within the carbon black industry. The problem has been shown to be
related to the slow process of chemisorbing oxygen on the surfaces of carbon black at ambient conditions.
A solution to this problem using partially graphitized carbon black has been recognized, demonstrated, and
pursued by D24 committee from a testing perspective.
.
RECOMMENDATIONS
The D24 committee recommends use of these precision statistics and control chart limits as they
are most current data available concerning the ASTM SRB B-6 and E-6 standards, along with the
experimental HT-B6 and HT-E6 standards.