Designation: D 6284 – 02

Standard Test Method for

Rubber Property—Effect of Aqueous Solutions with
Available Chlorine and Chloramine1
This standard is issued under the fixed designation D 6284; 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 3.2 combined residual chlorine—residual consisting of

1.1 This test method covers procedures for evaluating the chlorine combined with ammonia nitrogen and nitrogenous
ability of rubber and rubber-like materials to withstand the compounds.
effects of aqueous solutions with available chlorine and 3.3 free available chlorine residual—residual consisting of
chloramine. It is intended to compare the effects of chlorine hypochlorite ions (OCI) or hydrochlorous acid (HOCl), or
compounds, present in potable water due to disinfection both.
procedures, on rubber articles. 3.4 total residual chlorine (chlorine residual)—the amount
1.2 Test solutions are designed to contain chlorine com- of available chlorine-induced oxidants present in water at any
pounds, including hypochlorous acid (HOCI), hypochlorite specified period, subsequent to the addition of chlorine.
ions (OCI), and monochloramine (NH2Cl). 4. Summary of Test Method
1.3 This standard does not purport to address all of the
safety concerns, if any, associated with its use. It is the 4.1 This test method provides procedures for exposing test
responsibility of the user of this standard to establish appro- pieces to aqueous available chlorine and chloramine solutions
priate safety and health practices and determine the applica- under defined conditions of temperature and time.
bility of regulatory limitations prior to use. 4.2 This test method includes the following procedures:
Change in mass after immersion Section 10
2. Referenced Documents Change in volume after immersion Section 11
Change in hardness after immersion Section 12
2.1 ASTM Standards: Visual and turbidity rating after immersion Section 13
D 471 Test Method for Rubber Property—Effect of Liq- 4.3 The resulting deterioration is measured by changes in
uids2 mass, volume, hardness, and appearance of the test piece
D 1193 Specification for Reagent Water3 surfaces and test liquid after immersion.
D 1253 Test Methods for Residual Chlorine in Water3 4.4 This test method also describes the preparation of the
D 1889 Test Method for Turbidity of Water3 immersion liquids.
D 2240 Test Method for Rubber Property—Durometer
Hardness2 5. Significance and Use
D 3182 Practice for Rubber—Materials, Equipment, and 5.1 Rubber articles, such as seals, gaskets, and membranes,
Procedures for Mixing Standard Compounds and Prepar- may be exposed in service to chlorine compounds used in
ing Standard Vulcanized Sheets2 potable water as disinfectants. The exposure may be intermit-
D 3183 Practice for Rubber—Preparation of Pieces for Test tent or continuous and can occur at various temperatures.
Purposes from Products2 5.2 Properties of rubber articles can deteriorate as a result of
D 4483 Practice for Determining Precision for Test Method exposure to water containing these chlorine compounds, af-
Standards in the Rubber and Carbon Black Industries2 fecting their performance for the intended use.
3. Terminology 5.3 This test method attempts to simulate service conditions
through controlled accelerated testing, but may not give a
3.1 The terminology of chlorine compounds used in this test direct correlation with part performance under actual service
method is in accordance with Test Methods D 1253, Section 7. conditions. It yields comparative data on which to base
judgement on expected service quality.
1
This test method is under the jurisdiction of ASTM Committee D11 on Rubber 5.4 This test method is suitable for compliance testing,
and is the direct responsibility of Subcommittee D11.40 on Consumer Rubber quality control, and research and development work.
Products.
Current edition approved Dec. 10, 2002. Published December 2002. Originally
approved in 1998. Last previous edition approved in 1998 as D 6284 – 98.
2
Annual Book of ASTM Standards, Vol 09.01.
3
Annual Book of ASTM Standards, Vol 11.01.

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

1
 D 6284 – 02
TABLE 1 Immersion Periods, h (158 6 4°F) prior to transferring them into test vessels in
22 670 accordance with Section 9.
46 1006 8.4.1 An acceptable alternative method is the use of a glass
70 1342
166 2186 container of sufficient volume to prepare a large batch of test
334 4366 solution capable of filling all test vessels with 1900 cm3 of
502 solution each. Prior to filling the test vessels, the liquid shall be
stirred and checked with an immersion thermometer to ensure
that the specified test temperature has been reached throughout
6. Test Conditions the batch.
8.5 Preparation of Standard Test Liquids and Solutions:
6.1 Temperature—Unless otherwise specified between the
8.5.1 Reagent Water—Distilled or deionized water (Type III
producer and the purchaser, the preferred test temperature shall
or purer, see Specification D 1193) is heated to the test
be 70 6 2°C (158 6 4°F).
temperature in a loosely sealed amber glass jar and transferred
6.1.1 If the temperature of the testing room is other than the
to the test vessel.
standard 23 6 2°C (73 6 4°F), the actual room temperature
8.5.2 Available Chlorine Test Solution—A volume of 1900
and any effect on the temperature of the test liquids shall be
cm3 of distilled or deionized water (Type III or purer, see
reported.
Specification D 1193) is heated to the test temperature in a
6.2 Immersion Periods—Unless otherwise specified, the
loosely sealed amber glass jar and 0.9 cm3 of sodium hy-
immersion periods shall be as indicated in Table 1, depending
pochlorite solution with 10 % minimum total residual chlorine7
on the anticipated service conditions.
and 7.0 cm3 of phosphate buffer solution8 (pH 7.0) are then
6.2.1 To obtain a measure on the rate of deterioration, it is
added, using a graduated pipet. The glass jar is again condi-
necessary to take measurements after several immersion peri-
tioned for 10 6 1 min at the specified test temperature and the
ods. The tolerance of the immersion times shall be 615 min or
solution transferred into the test vessel. Solution strength shall
61 % of the specified time, whichever is greater.
be 50 ppm (mg/L) of total residual chlorine determined in
7. Apparatus accordance with Test Methods D 1253, Section 10. The deter-
mination of free available chlorine residual and combined
7.1 A three-necked flask4 with a capacity of 2000 cm3 shall available chlorine residual for informational purposes is op-
be mounted in an electric heating mantle5 of sufficient size and tional.
wattage to maintain the specified temperature throughout the 8.5.2.1 Chloramine T shall not be used as a replacement for
test solution. The center neck of the flask shall be used for any of the reagents specified in the preparation of the test
inserting and removing test pieces and shall be fitted with a solutions.
removable glass stopper. The other two necks of the flask shall 8.5.2.2 Sodium hypochlorite solutions are not stable and
be tightly fitted with an immersion thermometer and a Graham will change their concentration in storage. It is therefore
condenser6 with continuous cooling water supply. recommended to use fresh solutions or store solutions in the
7.2 Test procedures utilizing continuous monitoring of test dark under refrigeration (about 5°C (41°F)). The concentration
liquids and automatic addition of reagents may be used but can of solutions stored for any length of time should be confirmed
be expected to produce different results than those obtained by by determining their total residual chlorine level in accordance
the procedures of this test method. with Test Methods D 1253, Section 10. If the concentration has
changed, the necessary adjustments shall be made in the
8. Standard Test Liquids
preparation of the test solutions.
8.1 Standard test liquids are prepared in amber glass jars of 8.5.3 Monochloramine Test Solution—A volume of 1900
sufficient volume to hold 1900 cm3 of the liquid. cm3 of distilled or deionized water (Type III or purer, see
8.2 Fresh test solutions shall be prepared on a daily basis. At Specification D 1193) is heated to the test temperature in a
no time throughout the entire test period shall test pieces be loosely sealed amber glass jar and 0.9 cm3 of sodium hy-
allowed to remain in the same solution for more than 48 h. pochlorite solution with 10 % minimum total residual chlorine7
8.2.1 If the test period is to be 166 h or greater, the test and 4.0 cm3 of phosphate buffer solution8 (pH 7.0) are then
solutions shall be left unchanged for one day per week. added, using a graduated pipette. The glass jar is conditioned
8.3 Total residual chlorine levels of at least one freshly for 10 6 1 min at the specified test temperature followed by the
prepared available chlorine and monochloramine solution shall addition of 2.7 cm3 1N ammonium hydroxide9 and 8.0 cm3 of
be determined weekly. phosphate buffer solution8 (pH 7.0). The glass jar is again
8.4 Test solutions are heated in loosely sealed amber glass conditioned at the test temperature for 10 6 1 min and the
jars in a suitable water bath or hot forced-air oven to 70 6 2°C finished solution transferred to the test vessel. Solution strength

4 7
A suitable flask can be obtained under Catalog No. 4960-2L from Corning, Inc., A suitable solution can be obtained under Catalog No. 7216 from Mallinckrodt,
County Rd. 64, Big Flats, NY 14814. Inc., Highway 68 Bypass, Paris, KY 40361.
5 8
A suitable heating mantle can be obtained under Catalog No. EM-2000C from A suitable buffer solution can be obtained under Catalog No. 27002 from Hach
Electrothermal, Inc., 275 Morristown Rd., Gillette, NJ 07933. Co., 5600 Lindburgh Drive, Loveland, CO 80538.
6 9
A suitable condenser can be obtained under Catalog No. 2560-500 from A suitable solution can be obtained under Catalog No. V 044 from Mallinck-
Corning, Inc., County Rd. 64, Big Flats, NY 14814. rodt, Inc., Highway 68 Bypass, Paris, KY 40361.

2
 D 6284 – 02
TABLE 2 Dimensions of Standard Specimens perforated glass beads. It is important that the materials used to
Type Length, mm (in.) Width, mm (in.) Thickness, mm (in.) suspend and separate the test pieces do not affect the test liquid
1 50.0 6 0.1 25.0 6 0.1 1.0 6 0.1 and the rubber.
(2.000 6 0.004) (1.000 6 0.004) (0.040 6 0.004) 10.4 Place the test piece setup in the test vessel (see 9.1)
2 50.0 6 0.1 25.0 6 0.1 2.0 6 0.1
(2.000 6 0.004) (1.000 6 0.004) (0.080 6 0.004) containing the test liquid for the specified time and remove
3 50.0 6 0.1 25.0 6 0.1 4.0 6 0.1 each test piece from the flask at the end of the immersion
(2.000 6 0.004) (1.000 6 0.004) (0.160 6 0.004)
period.
10.5 Cool the test pieces to room temperature by transfer-
ring them into a cool and clean portion of the test liquid for 30
min. After removal from the liquid, lightly blot the test pieces
shall be 50 ppm (mg/L) of total residual chlorine determined in
dry with lint-free paper, place them in a tared stoppered
accordance with Test Methods D 1253, Section 10. The deter-
weighing bottle, weigh each test piece to the nearest 1 mg,
mination of free available chlorine residual and combined
record the mass as M2.
available chlorine residual for informational purposes is op-
tional. 10.6 Return the test pieces to the cool and clean portion of
8.5.3.1 Chloramine T shall not be used as a replacement for the test liquid before proceeding with hardness testing and
any of the reagents specified in the preparation of the test visual rating. After completing all testing return the test pieces
solutions. to the test vessel with the same test liquid, if data are desired
8.5.3.2 Sodium hypochlorite solutions are not stable and on progressive changes that occur with increasing immersion
will change their concentration in storage. It is therefore times.
recommended to use fresh solutions or store solutions in the 10.7 It is important that each manipulation following re-
dark under refrigeration (about 5°C (41°F)). The concentration moval of the test pieces from the test liquid takes place
of solutions stored for any length of time should be confirmed promptly with the least possible lapse in time.
by determining their total residual chlorine level in accordance 10.8 Prepared fresh test liquids daily in accordance with 8.2,
with Test Methods D 1253, Section 10. If the concentration has except as described in 2.1. Discard the old solutions after
changed, the necessary adjustments shall be made in the evaluating turbidity and add fresh solutions to the test vessel
preparation of the test solutions. (without removal of the test pieces).

9. Test Specimens 11. Procedure for Change in Volume

9.1 Unless otherwise specified, test pieces shall be prepared 11.1 See Test Method D 471, Section 11.
in accordance with Practice D 3182 or Practice D 3183. 11.2 Test three test pieces of a single composition. Calculate
9.2 Dimensions of standard test pieces shall be as indicated the test results of the three test pieces in accordance with Eq 2
in Table 2. Type 2 specimens shall be cut from standard and average the results.
vulcanized sheets prepared in accordance with Practice 11.3 Weight each test piece in air to the nearest 1 mg and
D 3182. Sheets for Type 1 and 3 specimens shall be vulcanized record the mass as M1. Then obtain the mass M2 of each test
in molds modified for cavity depth, but having otherwise the piece immersed in distilled water or methanol (Note 1) at room
same dimensions as specified in Practice D 3182 (Fig. 1, 2, 3, temperature.
or 4).
9.3 Type 1 specimens are preferred for accelerated testing. NOTE 1—Methanol may be employed in place of water if the removal
Types 2 and 3 specimens may be specified by mutual agree- of air bubbles from the test piece surface is a problem.
ment between the producer and the purchaser. 11.4 Quickly blot the test pieces dry using lint-free paper,
9.4 The same test pieces are used to determine changes in mount three test pieces on a glass rod in accordance with 10.3,
mass, volume, hardness, and visual rating. and place the test piece setup in the test vessel (see 9.1)
9.5 If rubber parts or nonstandard test pieces are used, the containing the test liquid for the specified time.
procedure shall be adjusted to maintain a minimum volume of 11.5 Remove each test piece from the flask at the end of the
20 cm3 of test solutions per 1 cm2 of test piece surface area. immersion period and cool to room temperature in a cool and
Data obtained on test pieces of different original thicknesses clean portion of the test liquid for 30 min. Lightly blot each test
are not comparable. piece dry with lint-free paper, place it in a tared stoppered
weighing bottle, weigh to the nearest 1 mg, and record the mass
10. Procedure for Change in Mass as M3. Remove each test piece from the weighing bottle, weigh
10.1 See Test Method D 471, Section 10. in distilled water or methanol to the nearest 1 mg, and record
10.2 Test three test pieces of a single composition. Calculate the mass as M4.
the test results of the three test pieces in accordance with Eq 1 11.6 Return the test pieces to the cool and clean portion of
and average the results. the test liquid before proceeding with hardness testing and
10.3 Weigh each test piece in air to the nearest 1 mg, record visual rating. After completing all testing return the test pieces
the mass as M1, and mount three test pieces on a glass rod so to the test vessel with the same test liquid, if data are desired
that a minimum of 6-mm (0.25-in.) separation is maintained on progressive changes that occur with increasing immersion
between the test pieces through the use of spacers, for example, times.

3
 D 6284 – 02
11.7 It is important that each manipulation following re- M1 = initial mass of test piece in air, g, and
moval of the test pieces from the test liquid takes place M 2 = mass of test piece in air after immersion, g.
promptly with the least possible lapse in time. 14.2 Calculate the percent change in volume as follows
11.8 Prepare fresh test liquids daily in accordance with 8.2, (Section 11):
except as described in 2.1. Discard the old solutions after ~ M3 2 M4 ! 2 ~ M1 2 M2 !
evaluating turbidity (Section 13) and add fresh solutions to the D V, % 5 • 100 (2)
~ M1 2 M2 !
test vessel (without removal of the test pieces).
where:
12. Procedure for Change in Hardness DV = change in volume, %,
12.1 See Test Method D 471, Section 15. M1 = initial mass of test piece in air, g,
12.2 Measure hardness in accordance with Test Method M2 = initial mass of test piece in water or methanol, g,
D 2240. M3 = mass of test piece in air after immersion, g, and
M4 = mass of test piece in water or methanol after
12.3 Ply Up Three Standard Test Pieces (Section 9) for
immersion, g.
measuring hardness before and after immersion. Make hard-
14.3 Calculate the hardness change in hardness units as
ness measurements as close as possible to the center of the test
follows (Section 12):
pieces.
12.4 Measure the hardness of the top piece and then place it DH 5 Hj 2 Ho (3)
to the bottom of the stack. Repeat the same procedure for the
where:
remaining two test pieces and report the median of the three DH = hardness change after immersion, units,
readings. The time interval between removal from the cooling H o = initial hardness, units, and
liquid and testing shall not be less than 2 nor more than 3 min. Hj = hardness after immersion, units.
12.5 The hardness before immersion is referred to as HO and
the hardness after immersion as Hj. Calculate hardness change 15. Report
in accordance with Eq 3.
15.1 State that the test was conducted in accordance with
12.6 If data on progressive changes with increased immer-
Test Method D 6284 and report the following information:
sion times are required, return the test pieces to the vessel with
15.1.1 Description of the sample and its origin,
the same test liquid.
15.1.2 Date and temperature of testing room,
15.1.3 Duration, temperature, and date and vulcanization of
13. Procedure for Visual and Turbidity Rating
test pieces,
13.1 Inspection of Test Piece Surface: 15.1.4 Dates of the various periods of exposure,
13.1.1 Visually examine the surface appearance of im- 15.1.5 Type of immersion liquid(s) used,
mersed test pieces for signs of progressive degradation in 15.1.6 Temperature and duration of exposure,
comparison to an unexposed test piece or control specimen of 15.1.7 Test results on weight, volume, and hardness changes
known degradation. Note and record changes in the test piece after immersion,
surface. 15.1.8 Visible changes of test piece surface after immersion,
13.1.2 If data on progressive changes with increased immer- 15.1.9 Turbidity of immersion liquid(s) in nephelometric
sion times are required, return the test pieces to the vessel with turbidity units (NTU), and
the same test liquid. 15.1.10 Any deviation from standard test methods.
13.2 Turbidity of Test Liquid:
13.2.1 This test is used to determine the progressive degra- 16. Precision and Bias
dation that has occurred in the test pieces since the last test
16.1 The interlaboratory test program (ITP) for this standard
liquid change.
was not executed according to the guidelines as set forth in
13.2.2 At least 24 h after the last test liquid change, remove
Practice D 4483. It was a simplified program that did not
the test pieces from the solution, vigorously shake the solution
conduct replicate test result measurements within any labora-
in the flask for a minimum of 2 min and immediately remove
tory in the program. For any normal evaluation of precision,
a sample of the liquid for turbidity testing in accordance with
these replicate test result measurements, usually obtained in a
Test Method D 1889.
day–1 versus day–2 sequence for duplicates, are required for
13.2.3 Record and report readings in nephelometric turbid-
the evaluation of repeatability.
ity units (NTU).
16.2 The ITP was conducted during the time period 1998-
2000 using five different rubber compounds: (1) FKM, (2)
14. Calculation
EPDM/polypropylene thermoplastic vulcanizate, (3) sulfur
14.1 Calculate the percent change in mass as follows vulcanized SBR, (4) peroxide vulcanized NBR, and (5) sulfur
(Section 10): vulcanized EPDM.
~ M2 2 M 1 ! 16.2.1 Each of these was tested once for volume swell,
D M, % 5 3 100 (1)
M1 using four different immersion/aging periods: 1, 2, 3 and 4
weeks at 70°C. Other physical properties were not part of the
where: ITP. A test result is the average for three test specimens as
DM = change in mass, %,
specified in 11.2. Only four laboratories volunteered for the

4
 D 6284 – 02
program. This is an inadequate number for a valid evaluation of TABLE 3 Estimated Type 1 Precision
precision. The data that have been obtained have been used NOTE—Property = Percent volume swell at 70°C as mean value for 4
however to obtain the best possible estimate for repeatability weeks immersion.
and reproducibility for this particular program. The values for Material Mean Sr r (r) SR R (R) No. Labs
reproducibility that are given below can be considered as Cmpd. B 4.4 0.11A 0.30A 6.3A 0.37 1.05 22.9 4
approximate. The special values for repeatability are estimated Cmpd. A 8.6 0.30 0.83 9.0 5.02 14.04 172.5 4
as discussed below. Cmpd. E 16.3 0.81 2.3 17.0 1.6 4.4 36.6 2
Cmpd. D 26.2 3.3 9.2 53.5 18.5 51.8 99.3 3
16.3 The precision results as determined by this ITP may Cmpd. C 49.4 2.1 5.8 13.3 8.2 22.9 35.3 3
not be applied to acceptance or rejection testing for any group A
These columns are only estimated; see text of standard for details.
of materials or products without documentation that the results Sr = Estimated repeatability standard deviation, units: % swell.
of this precision evaluation actually apply to the products or r = estimated repeatability, in measurement units, % swell.
(r) = estimated relative repeatability, percent of percent.
materials tested. SR = reproducibility standard deviation, units: % swell (approximate value).
16.4 Special Repeatability Estimation—Since no repeat (R) = relative reproducibility, percent of percent (approximate value).
measurements were conducted in any laboratory, an estimate of
the repeatability has been made as follows. The volume swell 16.5 Repeatability—The approximate repeatability, or local
was plotted versus time. All plots had a good linear character. domain precision, of this test method has been established by
A simple regression analysis was conducted for each material. the values found in Table 3 for each of the materials as listed
The correlation coefficients were all high (0.98 or better) and in the table. Two single test results (obtained by the proper use
from the regression the standard deviation of the estimate was of this standard) that differ by more than the tabulated values
evaluated with 2 DF. This standard deviation of the estimate for r, in measurement units, and (r), in percent, shall be
was equated with the average or mean standard deviation in considered as suspect, that is, to have come from different
measuring volume swell over the period 1 to 4 weeks. populations. Such a decision suggests that some appropriate
investigative action be taken. See explanation for the repeat-
16.4.1 Once values for repeatability standard deviation (of
ability as described in 16.4.
estimate) were obtained for each material, they were used to
16.6 Reproducibility—The approximate reproducibility, or
calculate duplicate values for each immersion period and from
global domain precision, of this test method has been estab-
this and the single percent swell values, as reported by each
lished by the values found in Table 3 for each of the materials
laboratory, the basic data tabulation tables that are required for
as listed in the table. Two single test results obtained in
calculating r and R were generated. The data in these tables
different laboratories (by the proper use of this standard) that
were then used to calculate r, (r), R, and (R) for each material
differ by more than the tabulated values for R, in measurement
by the new revised precision evaluation standard. This new units, and (R), in percent, shall be considered as suspect, that is,
standard is a revised version of Practice D 4483 and was to have come from different populations. Such a decision
published in 2002. suggests that some appropriate investigative action be taken.
16.4.2 Since (1) an average repeatability has been used, and See comments on reproducibility in 16.2.1.
(2) an insufficient number of laboratories participated in this 16.7 Bias—Bias is the difference between a test value and a
ITP to give really definitive values, the final precision as given reference or true value. Reference values do not exist for this
in Table 3 are average values over the immersion periods of 1, test method, therefore bias cannot be determined.
2, 3 and 4 weeks. The relative repeatability precision (r) varies
over the range of 6 to 54 % and the relative reproducibility 17. Keywords
precision (R) has a range of 23 to 199 %. Compounds A and D 17.1 available chlorine; chloramine; chlorine; disinfection;
have very poor reproducibility. plumbing; potable water

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