Designation: D 6845 – 02

Standard Test Method for

Silica, Precipitated, Hydrated—CTAB
(Cetyltrimethylammonium Bromide) Surface Area1
This standard is issued under the fixed designation D 6845; 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 (e) indicates an editorial change since the last revision or reapproval.

1. Scope nate (Aerosol OT4) solution to a turbidity maximum end point

1.1 This test method covers the measurement of the specific is used to determine the unadsorbed CTAB after removal of the
surface area of precipitated silicas exclusive of area contained colloidally dispersed silica by ultrafiltration.
in micropores too small to admit hexadecyltrimethylammo- 3.2 Titration of the unadsorbed CTAB with Aerosol OT
nium bromide (cetyltrimethylammonium bromide, commonly solution is accomplished by automatic titration.
referred to as CTAB) molecules. This test method is suitable
4. Significance and Use
for characterizing rubber-grade silicas of all types.
1.2 The values stated in SI units are to be regarded as the 4.1 The CTAB molecule is relatively large; so it is not
standard. The values given in parentheses are for information adsorbed in micropores or on surface roughness. Thus, the
only. CTAB surface area reflects only the surface of the silica that is
1.3 This standard does not purport to address all of the available for interaction with rubber molecules.
safety concerns, if any, associated with its use. It is the 5. Apparatus
responsibility of the user of this standard to establish appro-
priate safety and health practices and determine the applica- 5.1 Analytical Balance, 0.1 mg sensitivity.
bility of regulatory limitations prior to use. 5.2 Centifuge, capable of 67 rev/s (4000 r/m).
5.3 Magnetic Spinbars,5 chemically resistant covered (poly-
2. Referenced Documents chlorotrifluoroethylene or TFE-fluorocarbon), 6.4- or 4.8-mm
2.1 ASTM Standards: (1⁄4- or 3⁄16-in.) diameter, and length nearly equal to the
D 1193 Specification for Reagent Water2 diameter of 50 or 100 cm3 Berzelius beakers, glass vials, or
D 1799 Practice for Carbon Black—Sampling Packaged other glass vessels.
Shipments3 5.4 Glass Funnel, small.
D 1900 Practice for Carbon Black—Sampling Bulk Ship- 5.5 Glass Vials, with plastic screw caps, 28 mm in outside
ments3 diameter, about 40 cm3 capacity.
D 4483 Practice for Determining Precision for Test Method 5.6 Buret, 50 cm3, 0.1 cm3 divisions, Class A, preferably of
Standards in the Rubber and Carbon Black Industries3 automatic refilling and zeroing type (see Note 1) with reagent
reservoir.
3. Summary of Test Method NOTE 1—Automatic burets are usually not certified to Class A toler-
3.1 The isotherm for adsorption of an aqueous solution of ance. Such burets should be checked for accuracy, and if in error by more
CTAB on silicas has a long horizontal plateau corresponding to than 0.05 cm3 at any point, a calibration curve should be prepared and
a monolayer coverage of the substrate surface from which the used to correct observed buret readings. Burets with TFE-fluorocarbon
adsorbate is not sterically excluded. The CTAB adsorption by manostat valves offer some advantage in ease of stopcock manipulation in
delivering small increments of titrant.
silica is independent of functional groups containing hydrogen
and oxygen, etc. Rapid equilibration is achieved by using 5.7 Dispenser-Type Pipet,6 50 cm3, attached to a suitable
mechanical stirring. Titration with dioctyl sodium sulfosucci- reservoir for CTAB solution.

1 4
This test method is under the jurisdiction of ASTM Committee D11 on Rubber Aerosol OT is a registered trademark of the American Cyanamid Co., Process
and is the direct responsibility of Subcommittee D11.20 on Compounding Materials Chemicals Dept., Wayne, NM 07470.
5
and Procedures. Examples of suitable spinbars are Catalog No. 9235-U7, A. H. Thomas Co.,
Current edition approved Dec. 10, 2002. Published December 2002. Originally Philadelphia, PA 19105, or Catalog No. S-76497-30, Sargent Welch Scientific Co.,
approved in 2002. Last previous edition approved in 2002 as D 6845 – 02. Skokie, IL 60076.
2 6
Annual Book of ASTM Standards, Vol 11.01. This test is based on the use of the Universal Repipet, a registered trademark
3
Annual Book of ASTM Standards, Vol 09.01. of Labindustries, 1802 Second St., Berkeley, CA 94710.

Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.

1
 D 6845 – 02
5.8 Pipet, 10 cm3, Class A. Homogenize on a magnetic stirrer for 10 h. Allow to stand 24
5.9 Erlenmeyer Flasks, or beakers, 50 or 100 cm3. h before use. Verify that the pH of the solution is 9.6 6 0.1
5.10 Dropping Bottle, 60 cm3 amber. before use. If not, adjust the pH with either 0.1 N NaOH
5.11 Jar, wide-mouth, plastic screw cap, 120 or 240 cm3 (4- solution (too low) or 0.1 N HCl solution (too high).
or 8-oz) size. (Warning—Storage of the solution below 22°C will result in
5.12 Gravity Convection Drying Oven, capable of maintain- slow crystallization of the CTAB.)
ing 105 6 5°C. 6.6 Aerosol OT10 Solution 100 % Grade (approximately
5.13 Magnetic Stirrer. 0.00389 M)—Dissolve 1.73 g/dm3 of Aerosol OT solution
5.14 Containers, suitable for preparation and storage of (100 % solids) in 500 cm3 distilled or deionized water. Stir
reagent solutions. vigorously with a magnetic stirrer for 10 h. Allow to stand an
5.15 Automatic Titration Equipment with 550 nm Photo- additional twelve days before standardization and use. The
probe,7 with instruction manual. solution should be capped tightly and stored in a cool place.
5.16 Beakers, 100 cm3 Berzelius, tall form (one furnished (Once opened, 100 % Aerosol OT should be stored in a
with automatic titration equipment). desiccator.)
5.17 Thermometer, to measure temperature in a range from 6.7 Distilled or Deionized Water.
20 to 40°C. 6.8 Octylphenoxy Polyethoxyethanol (Triton X-10011) Solu-
5.18 Polyethylene Tubing (do not use vinyl tubing). tion (0.15 %)—Dissolve 1.5 g in 1 dm3 of Triton X-100 (100 %
liquid) in distilled or deionized water by swirling vigorously
NOTE 2—All apparatus must be kept chemically clean. Contamination
of equipment, water supply, or chemicals by ionic surfactants must be with a magnetic stirrer until a homogeneous solution is
particularly avoided. obtained.

6. Reagents 7. Sampling
6.1 Purity of Reagents—Reagent grade chemicals shall be 7.1 No separate practice for sampling silicas is available.
used in all tests. Unless otherwise indicated, it is intended that However, samples may be taken in accordance with Practices
all reagents conform to the specifications of the Committee on D 1799 or D 1900.
Analytical Reagents of the American Chemical Society where
such specifications are available.8 Other grades may be used, 8. Standardization of Reagents
provided it is first ascertained that the reagent is of sufficiently 8.1 Duplicate blanks are determined and averaged.
high purity to permit its use without lessening the accuracy of 8.2 Pipet 10 cm3 of CTAB solution into a beaker.
the determination. 8.3 Add 50 cm3 of distilled or deionized water.
6.2 Purity of Water—Unless otherwise indicated, references 8.4 Titrate with Aerosol OT using automatic titrator until
to water shall be understood to mean reagent water as defined endpoint is reached.
by Type 1 in Specification D 1193. 8.5 Use average of both repetitions when calculating CTAB
6.3 Sodium Hydroxide Solution (1M)—Dissolve 40.0 g of silica sample in Section 10.
NaOH in a 1 dm3 flask containing 0.5 dm3 reagent water. After
dissolution fill to mark. 9. Procedure
6.4 Buffer Solution of pH 9.6 (0.05 M)—Prepare buffer 9.1 Dry an adequate portion of sample of silica at 105°C for
solution by dissolving 3.101 g of orthoboric acid (H3BO4), 2 h and cool in a desiccator.
3.708 g of potassium chloride (KCl) and 36.85 cm3 of sodium
hydroxide (NaOH) solution in a 1 dm3 flask containing 0.5 dm3 NOTE 3—If the heating loss of the silica is known, the drying step may
be omitted and the observed sample mass corrected for heating loss to
reagent water. After dissolution fill to mark. Verify that the pH obtain the mass of dry sample, W.
of the solution is 9.6 6 0.1.
6.5 CTAB Standard Solution—Dissolve 5.5 g of reagent- 9.2 Weigh, to 0.1 mg, a suitable sample of the dried silica
grade CTAB9 in a 1 dm3 flask containing 350 dm3 of buffer into a glass vial and record the mass as W. Appropriate sample
solution and 500 dm3 water. After dissolution fill to mark. masses may be selected as follows:
Approximate Surface Sample Mass,
Area, m2/g (SA) g
SA # 90 0.600
7
This test is based on the use of two sources of automatic titration equipment: 90 < SA # 120 0.500
(1) Mettler Memotitrator DL21, Mettler Instrument Co., Box 71, Highstown, NJ 120 < SA # 175 0.400
08520, and (2) Brinkman Dosimat 665 Buret, Brinkman Instruments, Inc., Canti- 175 < SA # 220 0.300
ague Rd., Westbury, NY. The Probe Colorimeter, also available from Brinkman 220 < SA 0.200
Instruments, has been found to be an acceptable automatic means of detecting the An appropriate sample mass may also be taken as Vo/Sest in
titration end point. This piece of equipment may be integrated with the Brinkman
Dosimat 665 Buret. g, where Sest is some estimate of the expected CTAB surface
8
Reagent Chemicals, American Chemical Society Specifications, Am. Chemical area.
Soc., Washington, DC. For suggestions on the testing of reagents not listed by the
American Chemical Society, see Reagent Chemicals and Standards, by Joseph
Rosin, D. Van Nostrand Co., Inc., New York, NY, and the United States Pharma-
10
copeia. Available from American Cyanamid Co., Process Chemicals Dept., Wayne,
9
Available from J. T. Baker Chemical Co., 222 Red School Lane, Phillipsburgh, NM 07470. Also available as Catalog No. A-349 from Fisher Scientific Co.
11
NJ 08865, Catalog No. 7N121. Triton X-100 is a registered trademark of Rohm and Haas Co.

2
 D 6845 – 02
9.3 Insert a magnetic spinbar into the vial. Add 30.0 cm3 of 9.8.7 Move the pump control to “flush” and allow a few
CTAB solution from the dispensing pipet or buret taking care drops of titrant to clear the needle. After the pump stops, close
to prevent foaming of the solution. Cap the vial. the stopcock and remove the needle from the beaker. Wipe the
9.4 Place the vial on a magnetic stirrer. Adjust the stirrer to needle with a clean tissue (do not use solvent).
give a vigorous stirring by the spinbar to produce a deep votex 9.8.8 Remove and rinse the photoprobe with distilled water.
without foaming. Stir for 40 min. 9.8.9 The unit is now ready for another sample.
9.5 Immediately after completion of the stirring, decant the
suspension into a centrifuge tube. 10. Calculation
9.6 Separate the silica from the suspension by centrifuging 10.1 Calculate the CTAB surface area to the nearest 0.1 3
for 20 min at 4000 rpms. 103 m2/g as follows:
9.7 Pipet a 10.00 cm3 aliquot of the CTAB solution from the S 5 ~2V0 2 V! 3 4774 / @V0 3 W~100 2 Vol!# (1)
centrifuge tube into a 100 cm3 beaker containing a TFE-
fluorocarbon covered magnetic spin bar 41 mm long by 10 mm where:
in diameter (1.625 by 0.375 in.), taking care to avoid transfer- S = CTAB surface area of dried silica, 103 m2/g,
ring any silica. V0 = volume of OT required to titrate 5 cm3 of CTAB
9.8 Titration (Automatic): (Blank),
9.8.1 Prepare the automatic titration apparatus according to V = aerosol OT solution required for the 10 cm3 sample,
the instructions furnished with it. Ascertain that the titrant W = sample mass, g, and
reservoir contains sufficient Aerosol OT solution and that the Vol = volatile matter of silica, %.
fluid lines and the pump head are free of air bubbles and have
11. Report
been flushed sufficiently with titrant. Turn the power on and
loosen the titrant reservoir cap to admit air as liquid flows out. 11.1 Report the following information:
Adjust the titrant flow rate to 10 cm3/min. 11.1.1 Proper identification of the silica sample and
9.8.2 Lower the 550 nm photo probe into the solution. 11.1.2 Result obtained from an individual determination,
9.8.3 Lower the titrant delivery assembly so that the deliv- reported to the nearest 0.1 3 103 m2/g.
ery needle is just below the surface of the liquid and open the
titrant stopcock. 12. Precision and Bias
9.8.4 Set the pump control switch to the “titrate” position 12.1 Precision and bias statements have not been generated.
and press the “start” button.
9.8.5 After the system stops record the amount of OT 13. Keywords
dispensed. 13.1 cetyltrimethylammonium bromide; CTAB; silica; sur-
9.8.6 Raise the titrant delivery tube clear of the beaker. face area by CTAB method; turbidity titration

ASTM International takes no position respecting the validity of any patent rights asserted in connection with any item mentioned
in this standard. Users of this standard are expressly advised that determination of the validity of any such patent rights, and the risk
of infringement of such rights, are entirely their own responsibility.

This standard is subject to revision at any time by the responsible technical committee and must be reviewed every five years and
if not revised, either reapproved or withdrawn. Your comments are invited either for revision of this standard or for additional standards
and should be addressed to ASTM International Headquarters. Your comments will receive careful consideration at a meeting of the
responsible technical committee, which you may attend. If you feel that your comments have not received a fair hearing you should
make your views known to the ASTM Committee on Standards, at the address shown below.

This standard is copyrighted by ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959,
United States. Individual reprints (single or multiple copies) of this standard may be obtained by contacting ASTM at the above
address or at 610-832-9585 (phone), 610-832-9555 (fax), or service@astm.org (e-mail); or through the ASTM website
(www.astm.org).