Designation: F 2466 – 05

Standard Practice for

Determining Silicone Volatiles in Silicone Rubber for
Transportation Applications1
This standard is issued under the fixed designation F 2466; 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 cyclo dimethyl-siloxane. Other species present having GC

1.1 This practice covers a means to determine the percent retention times similar to those of the cyclics are assumed to be
silicone-producing volatiles present in heat-cured silicone silicone as well.
rubber and room temperature-cured silicones (RTV). 5. Apparatus
1.2 Silicone-producing volatiles contribute to fouling of
oxygen sensor systems used in the control of vehicle emis- 5.1 Gas Chromatograph, equipped with a dual column, dual
sions. thermal conductivity detectors, differential flow control, linear
1.3 This standard does not purport to address all of the temperature programming capability, and an appropriate 1 mV
safety concerns, if any, associated with its use. It is the potentiometric recorder. An alternative unit may be the equiva-
responsibility of the user of this standard to establish appro- lent of a Hewlett Packard 5880A, equipped with a flame
priate safety and health practices and determine the applica- ionization detector, or as agreed upon between producer and
bility of regulatory limitations prior to use. user.
5.2 Column, to be used with the first GC is 2.4 m by 0.32 cm
2. Referenced Documents stainless steel with a 5 % OV-101 coating and 80/100 Chro-
2.1 ASTM Standards: 2 mosorb W, HP. The HP 5880A type GC uses a column 60 m by
D 3182 Practice for Rubber—Materials, Equipment, and 0.25 mm with 0.25-1 µm DB-1 or SE30 fused silica capillary
Procedures for Mixing Standard Compounds and Prepar- column or equivalent.
ing Standard Vulcanized Sheets 5.3 Operating conditions for first GC type are:
5.3.1 Column—50 to 320°C at 10°C/min.
3. Summary of Practice 5.3.2 Injector—290°C.
3.1 This practice consists of four (4) basic steps: (1) the 5.3.3 Detector—290°C.
silicone is cured to its elastomeric form, (2) the volatiles are 5.3.4 He Flow Velocity—4 cm/s.
extracted from the cured material, (3) the extract is separated 5.3.5 Sample Size—40 µL.
and measured by gas chromatography (GC), and (4) the GC 5.4 Operating conditions for the alternative GC type are:
results are quantified using a siloxane calibration. 5.4.1 Column—60 to 250°C at 10°C/min.
5.4.2 Injector—250°C.
4. Significance and Use 5.4.3 Detector—300°C.
4.1 Use of this practice in conjunction with realistic maxi- 5.4.4 He Flow Velocity—1-2 mL/min (column flow).
mum volatility tolerance level can help minimize the risk of 5.4.5 Sample Size—1 µL.
oxygen sensor dysfunction from formed-in-place-sealants in 5.5 Helium or Nitrogen, for the carrier gas.
transportation applications. This practice provides a method for 5.6 Humidity Chamber, or controlled lab environment.
determination of percentage volatiles in silicone elastomers. 5.7 Wrist-Action Mechanical Shaker.
The volatile silicones from a commercial silicone are primarily 5.8 Analytical Balance, with glass draft shield capable of
0.0001 g accuracy.
5.9 30-mL Vials, flint glass, with screw cap (polyethylene
1
This practice is under the jurisdiction of ASTM Committee F03 on Gaskets and lined).
is the direct responsibility of Subcommittee F03.50 on Analytical Test Methods.
Current edition approved March 1, 2005. Published April 2005.
5.10 Syringe, capable of accurately delivering 20 6 0.1 µL
2
For referenced ASTM standards, visit the ASTM website, www.astm.org, or (no plastic elements used due to solvents used).
contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM 5.11 Solvents and standards used are pentane (99 %) and
Standards volume information, refer to the standard’s Document Summary page on dodecane (99 %), both spectral grade.
the ASTM website.

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

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 F 2466 – 05
5.12 Rigid Plates (glass or aluminum), 0.90 mm thick, for 8. Conditioning
cutting the wet formed-in-place sealant. 8.1 Allow RTV samples to cure for 24 h, but not to exceed
5.13 Automated devices shall be used for measuring and 72 h at 25°C and 50 6 10 % relative humidity.
calculating peaks.
9. Procedure
6. Test Specimens 9.1 Extraction—Pre-weigh each cured sample to 1.0 6 0.2
6.1 Heat-cured silicone rubber samples shall be procured g (record weight to the nearest 0.0001 g) and set aside.
from either actual production parts, or shall be compression- 9.2 Weigh 0.020 6 0.005 g of dodecane (record weight to
molded ASTM tensile plaques (Practice D 3182). Cure condi- the nearest 0.0001 g) and place sample into the 30-mL vial. To
tions of the tensile plaques shall mirror cure conditions used on this add 10 mL of pentane. Immediately place the pre-weighed
the production parts. sample into the vial, and seal the container to prevent evapo-
6.2 Room temperature-vulcanized (RTV) samples shall be rative loss. Weight precision is extremely important for repro-
prepared by spreading the liquid using a suitable device, into ducible results. The sample vial is placed on a wrist shaker for
consistent 0.90 6 0.20 mm plaques. Avoid entrapped air and 16 h.
knit lines when preparing the sample. NOTE 1—The sequence is important due to the volatility of the solvents.
6.3 Three 1-g samples shall be cut from the plaque. These used.
samples shall be taken from near one corner, at the center of the 9.3 Inject 20 µL into the GC injection port.
plaque, and near the corner at a diagonal from the first. 9.4 After the elution is complete (about 35 min) identify the
peaks and quantify them by integration using the following
7. Standard Solutions3 equations:
7.1 Add 0.1 g (weighed to the nearest 0.1 mg) of each pure RfDn ~Area Dn in chromatogram!
%Dn 5 x
cyclic (>98 %) to 1.0 g of dodecane (99 %) (weighed to the ~Area dodecane in chromatogram!
nearest 0.1 mg). Ten millilitres 6 0.1 mL pentane is added and ~Wt. dodecane in sample!
the container is sealed to prevent evaporation. New standard Perform the calculation for D4 – D10 x 100 (2)

mixtures should be prepared if existing one is more than seven RfD4210~Area unknown in chromatogram!
% Unknown 5 x
(7) days old. ~Area dodecane in chromatogram!
7.2 Calibration of the standard solution is achieved using ~Wt. dodecane in sample!
one of the two operating conditions (dependent on the type of RfD1210 5 Average response factors of D4210 x 100
GC) described in 5.3 and inject 1 µL (need verify use with SE (3)
30 column – will need to attenuate response or dilute solution) 9.4.1 Perform the calculation for all unknowns that elute
standard solution sample. Response factors for the individual between D4 and D10.
cyclics are calculated using the following equation: 9.4.2 % Siloxane Volatiles = Sum of % cyclics D4-10 and
Amt. Dn in standard solution sum of % unknowns eluting from D4–D10.
RfDn 5 Area Dn in chromatogram x
NOTE 2—Silicone volatiles below D5 may not be detected at their
Area dodecane in chromatogram correct levels due to their loss from the sealant as it cures for 24 h at 25°C
Wt. dodecane in standard solution (1) and 50 % relative humidity. Dodecane can mask D5 forms and the
beginning of the first unknown. Any D3 not lost would be masked by
7.3 Response factors for cyclic species vary in a relatively impurities in pentane. Weight precision is extremely important if the
linear manner from D5 through D10, so that response factors for results are to be reproducible.
cyclics net in the standard solution can be calculated from the
known response factors of the cyclics in the standard solution. 10. Reporting
7.4 All of the unknowns that appear in the analysis (between 10.1 Three data points shall be reported for each sample as
D4 and D10) are assumed to be dimethyl siloxanes. All % total volatiles.
unknowns are given, as response factors, the average response 10.2 Final results for siloxane should be expressed as
factor calculated for the difunctional cyclosiloxane monomers 0.00 %. Report D4 through D10 for total volatiles as cyclics
D4 through D10. plus unknowns (L4 through L10).
10.3 All observed and recorded data on which calculations
are based.
10.4 Date of the test, cure conditions, and thickness of the
3
The sole source of supply of the standards solutions known to the committee at sample.
this time is Ohio Valley Specialty Chemicals, 115 Industrial Road, Marietta, OH,
45750, 1-800-729-6972, Catalog number 34569/Cyclic Standard Kit D3 through 11. Keywords
D10. If you are aware of alternative suppliers, please provide this information to
ASTM International Headquarters. Your comments will receive careful consider- 11.1 percent volatiles; silicone; transportation and oxygen
ation at a meeting of the responsible technical committee,1which you may attend. sensor systems

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 F 2466 – 05
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