STSA – Life without CTAB
April 26, 2004
by
Ricky Magee
Columbian Chemicals Company
1
Outline
• Introduction
• Theory
• Results
• Comparison with CTAB surface area
• Surface Chemistry Effects
• New Developments
• Conclusions
2
Introduction
• Importance of Surface Area
• Traditional Surface Area Techniques
• Timeline of STSA at ASTM
3
Importance of Surface Area
• Surface area is one of the most important
characteristics of the carbon black.
• Surface area of carbon black is a function of particle
size, degree of aggregation and porosity. Therefore,
surface area alone is not a reliable measure of particle
size.
• In the absence of porosity, surface area values are an
indication of a carbon black’s particle size
(fundamental property).
• According to IUPAC convention, micropores are
characterized by diameters less than 20 Å or 2 nm.
4
Effect of Aggregation and Porosity
on Surface Area
100 m2/g 80 m2/g 400 m2/g
5
Traditional Surface Area Tests
Attribute CTAB Iodine NSA
Surface Type
Measured External Total Total
Affect of Oxidation Unknown Severe Minimal
Precision Poor Good Good
Difficulty High Low Low
Set-up Costs Medium Low High
6
Timeline of STSA at ASTM
• D5816 – STSA approved as ASTM standard in 1995.
• D1765 (CB Classification System)– In 1997, STSA was
added as a typical value in Table 1, with corresponding
CTAB values deleted.
• D6556 – Combined NSA (D4820) and STSA (D5816)
into a single standard in 2000. The NSA section was
modernized and data interpretation simplified.
• D3765 – In 2003, estimated CTAB values of SRB-6
carbon blacks was added to CTAB method.
7
Theory
• Nitrogen Adsorption
• Saturated Vapor Pressure
• de Boer t-values and Va-t plots
• Pore filling model
• Application of CB t Equation
8
Nitrogen Adsorption
• The concentration of nitrogen is expressed as
relative pressure (P/Po).
• A relative pressure of “0.0” is measured at
absolute vacuum, while a value of “1.0” is
measured at nitrogen’s saturated vapor
pressure (Po).
• The typical range for measuring NSA (BET) is
P/Po = 0.05 to 0.30.
9
Saturated Vapor Pressure
• Saturated vapor pressure is the pressure at
which nitrogen gas condenses.
• It is based on atmospheric pressure and the
temperature of the liquid nitrogen in the dewar.
• It is usually 10 - 20 mm Hg above ambient
pressure due to impurities.
• Critical for measuring accurate STSA values.
10
Saturated Vapor Pressure
Elevation
Sea Level 900 m
• Atm. Pressure 760 685
• Sat. Vapor Press. 775 700
• P/Po Value = 0.1 78 70
• P/Po Value = 0.2 155 140
• P/Po Value = 0.3 233 210
All values in mm Hg
11
Thickness Model
Small Particles Large Particle
12
Thickness Equations
13.99
de Boer t = 0.034 - log P/Po
CB t = 0.88 (P/Po)2 + 6.45 (P/Po) + 2.98
Carbon Black t curve based on N762
13
Va–t Plot
60
50
Vol. Ads. (cc/g)
40 90 m2/g
30
60 m2 /g
20
10 2
30 m /g
0
0 1 2 3 4 5 6 7 8 9
Thickness (Å)
14
Pore Filling Model
P/Po = 0.0 P/Po = 0.05
P/Po = 0.2 P/Po > 0.2
15
Adsorption Isotherms
140
N472
120
N110
Vol. Adsorbed (cc/g)
100 N326
80 N660
60
40
20
0
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9
16 Relative Pressure
Va–t Plot for Standard Carbon Blacks
based on CB t equation
120
P/P o = 0.2 P/P o = 0.5
N472
100
Vol. Adsorbed (cc/g)
80
N110
60
40 N326
20
N660
0
0 1 2 3 4 5 6 7 8 9 10 11 12
17 Thickness (Å)
Results
• STSA versus CTAB
• Surface Chemistry
• Precision Statements
18
Tread Carbon Blacks
NSA STSA CTAB
N110 135.3 119.7 123.6
N121 122.8 116.5 120.4
N220 116.0 107.7 109.5
N234 117.2 111.2 115.6
N330 76.6 74.7 80.0
N339 91.0 88.5 94.8
All values in m2/g
19
Carcass Carbon Blacks
NSA STSA CTAB
N539 38.4 37.7 41.0
N550 38.1 38.2 38.6
N650 36.4 35.3 38.9
N660 33.0 33.1 34.9
N762 25.7 25.7 26.9
N787 29.7 29.6 31.0
All values in m2/g
20
CTAB versus STSA
140
120
100
CTAB (m 2/g)
80
60
40
20
R2 = 0.9985
0
0 20 40 60 80 100 120 140
21 STSA (m2/g)
Effect of Surface Oxidation on
CTAB Measurements
Sample
#1 #2 #3
Oxygen (%) 2.0 1.9 1.5
STSA (m2/g) 86.4 85.7 90.8
CTAB (m2/g) 100.1 97.5 97.7
Difference -13.7 -11.8 -6.9
22
Effect of Surface Oxidation on
CTAB Measurements
Sample
#1 #2 #3
STSA (m2/g) 86.3 86.3 90.0
Initial Value 86.4 85.7 90.8
CTAB (m2/g) 87.3 85.9 89.2
Initial Value 100.1 97.5 97.7
Difference -1.0 0.4 0.8
23
Effect of Heat Treatment on
ASTM SRB-5
25
NSA
20 Iodine
%Change
15
10
0
N135 N330 N220 N762 N660 N683
24
Effect of Heat Treatment on
ASTM SRB-5
5.0
2.5
%Change
0.0
-2.5
-5.0
STSA
-7.5 CTAB
-10.0
N135 N330 N220 N762 N660 N683
25
Precision
N121 Control Chart
2.5
CTAB
Diff. From Mean (m2/g)
1.5 STSA
0.5
-0.5
-1.5
-2.5
1 5 9 12 16 20
26
Run #
Effect of Solution Aging
on CTAB Solutions
122
121
CTAB (m 2/g)
120
119
118
117
116
115
0 10 20 30 40 50 60
27 Run #
Surface Area Precision Study
from Original STSA Paper
Within Lab
Between Lab
6
5
Percent
4
3
2
1
0
NSA STSA CTAB
28
Potential Errors in
NSA/STSA Measurements
• Improper degassing time/temperature.
• Improper sample weight.
• Inaccurate or changing Po value.
29
NSA/STSA Control Chart
using ASTM B-6 (N220)
112.0
111.5
111.0
Mean = 109.6 ± 1.1
110.5
(ASTM = 110.0 ± 1.6)
110.0
109.5
109.0
108.5
108.0
107.5
Surface Area (m2/g)
107.0
106.5
106.0
105.5
105.0
104.5
104.0
103.5 Mean = 105.4 ± 2.1
103.0
102.5
(ASTM = 105.4 ± 2.9)
102.0
101.5
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31
Data collected over a 4 month period
30
NSA/STSA Control Chart with
Po Outliers Removed (P >20mm Hg)
112.0
111.5
111.0
Mean = 109.5 ± 1.1
110.5
(Previous = 109.6 ± 1.1)
110.0
109.5
109.0
108.5
108.0
107.5
Surface Area (m2/g)
107.0
106.5
106.0
105.5
105.0
104.5
104.0
103.5 Mean = 105.4 ± 1.5
103.0 (Previous = 105.4 ± 2.1)
102.5
102.0
101.5
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31
31
Effect of Dewar Stability
• A single sample of ASTM B-6 (N220) degassed at
300°C then run multiple times, measuring the Po after
each run using the standard Gemini (600 ml) and a
large volume (2 L) dewars.
32
Modified Gemini
33
Effect of Dewar Stability – 1 Hr.
Equilibration Time
NSA (m2/g) STSA (m2/g)
1 Hour Equil. Mean 3 Mean 3
Dewar #1 - Std (600 ml) 110.0 1.83 104.7 4.86
Dewar #2 - Std (600 ml) 110.0 1.23 104.3 2.16
Dewar #3 - Large (2 L)* 109.9 0.18 105.4 0.57
Dewar #3 - Large (+15 mm)* 109.9 0.15 105.3 0.33
34 * = Filled and covered overnight before analysis
Effect of Dewar Stability – 2 Hr.
Equilibration Time
NSA (m2/g) STSA (m2/g)
1 Hour Equil. Mean 3 Mean 3
Dewar #1 - Std (600 ml) 110.2 0.60 105.2 0.87
Dewar #2 - Std (600 ml) 109.9 0.99 104.2 1.95
Dewar #3 - Large (2 L)* 109.9 0.15 105.3 0.33
Dewar #3 - Large (+15 mm)* 109.9 0.15 105.3 0.33
35 * = Filled and covered overnight before analysis
Po Summary
• A minimum 2 hour dewar equilibration is required
(longer is better).
• Large volume dewars allow improved precision.
• Other Po options exist for newer, higher-end
instruments.
• Changes to D6556 are required based on this study.
36
Analysis Time
Standard Method Modified Method
Standard Value (D6556) (3 pt.)
Sample ID NSA STSA NSA STSA NSA STSA
(m2/g) (m2/g) (m2/g) (m2/g) (m2/g) (m2/g)
A-6 (N134) 143.9 135.7 142.1 133.7 142.7 133.7
B-6 (N220) 110.0 105.4 109.4 104.6 108.8 105.3
C-6 (N326) 78.3 79.2 78.3 79.1 77.6 79.8
D-6 (N762) 30.6 29.6 30.4 29.0 30.7 29.2
E-6 (N660) 36.0 35.1 35.5 34.7 35.1 33.8
F-6 (N683) 35.3 34.1 34.7 33.2 34.6 32.8
Mean Values 72.4 69.9 71.7 69.1 71.6 69.1
37
Analysis Time
Standard Method (D6556) Modified Method (3 pt.)
Sample ID Analysis Degassing Total Analysis Degassing Total
Time Time Time Time Time Time
(min.) (min.) (min.) (min.) (min.) (min.)
A-6 (N134) 33 30 63 20 10 30
B-6 (N220) 30 30 60 17 10 27
C-6 (N326) 23 30 53 17 10 27
D-6 (N762) 20 30 50 15 5 20
E-6 (N660) 19 30 49 15 5 20
F-6 (N683) 20 30 50 14 5 19
Mean Values 24.2 30.0 54.2 16.3 7.5 23.8
38
Conclusions
STSA provides the following advantages
over CTAB:
Improved precision and accuracy, provided
proper attention to Po
Less affected by surface oxidation
Less operator time
Measured simultaneously with NSA
39
No reagent preparation
