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