Designation: D 3189 – 99

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Reprinted from the Annual Book of ASTM Standards. Copyright ASTM

Standard Test Methods for

Rubber—Evaluation of Solution BR (Polybutadiene Rubber)1
This standard is issued under the fixed designation D 3189; 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 Using Rotorless Cure Meters3

1.1 These test methods specify the standard materials, test NOTE 1—The specific dated edition of Practice D 3040 that prevails in
formula, mixing procedures, and test methods for evaluation of these test methods is referenced in the precision section.
butadiene rubber (BR) made by polymerization in solution.
1.2 The values stated in SI units are to be regarded as the 3. Significance and Use
standard. The values in parentheses are for information only. 3.1 These test methods are intended mainly for referee
1.3 This standard does not purport to address the safety purposes but may be used for quality control of rubber
concerns, if any, associated with its use. It is the responsibility production. They may also be used in research and develop-
of the user of this standard to establish appropriate safety and ment work and for comparison of different rubber samples in a
health practices and determine the applicability of regulatory standard formula.
limitations prior to use. 3.2 These tests may be used to obtain values for customer
acceptance of rubber.
2. Referenced Documents
2.1 ASTM Standards: 4. Standard Test Formula
D 88 Test Method for Saybolt Viscosity2 4.1 Standard Formulas:
D 412 Test Methods for Vulcanized Rubber and Thermo- IRM- Quantity,
plastic Rubbers and Thermoplastic Elastomers— Tension3 SRM Parts by
Material No. Mass
D 1646 Test Method for Rubber—Viscosity, Stress Relax-
ation, and Pre-Vulcanization Characteristics (Mooney Vis- BR ... 100.00
A
cometer)3 Zinc oxide
A
3.00
Sulfur 1.50
D 2084 Test Method for Rubber Property—Vulcanization Stearic acid A
2.00
Using Oscillating Disk Cure Meter3 Current IRB A
60.00
D 2161 Practice for Conversion of Kinematic Viscosity to TBBSB A
0.90
ASTM Type 103 petroleum oilC A
15.00
Saybolt Universal Viscosity or to Saybolt Furol Viscosity4
Total 182.40
D 2501 Test Method for Calculation of Viscosity-Gravity Batch Factor for mill mixD 4.0
Constant (VGC) of Petroleum Oils4 Batch Factor for internal mixerD 7.13
D 3040 Practice for Preparing Precision Statements for Batch Factor for MIM Mix (Cam Head)D,E 0.40
Batch Factor for MIM Mix (Banbury 0.34
Standards Related to Rubber and Rubber Testing5 Head)D,E
D 3182 Practice for Rubber—Materials, Equipment, and A
Use the latest IRM/SRM.
Procedures for Mixing Standard Compounds and Prepar- B
N-tert-butyl-2-benzothiazolesulfenamide.
ing Standard Vulcanized Sheets3 C
Viscosity is 16.8 6 1.2 mm2/s at 100°C in accordance with Test Methods D 88
D 3896 Practice for Rubber from Synthetic Sources— and Practice D 2161. Viscosity Gravity Constant is 0.889 6 0.002 in accordance
with Test Method D 2501. Available in 1 and 5-gal (3.8 and 19-L) quantities from
Sampling3 Sun Oil, Industrial Products Dept., 1608 Walnut St., Philadelphia, PA 19103.
D 4483 Practice for Determining Precision for Test Method D
For mill and internal mixer batches, weigh the rubber, carbon black and oil to
Standards in the Rubber and Carbon Black Industries3 the nearest 1.0 g, the sulfur and accelerators to the nearest 0.02 g, and the other
D 5289 Test Method for Rubber Property—Vulcanization compounding materials to the nearest 0.1 g. For MIM batches, weigh the rubber
and material, blend to the nearest 0.01 g and the individual compounding
materials, if used, to the nearest 0.001 g.
E
1
For the MIM procedure, it is recommended that a blend of compounding
These test methods are under the jurisdiction of ASTM Committee D-11 on materials, excluding carbon black and oil, be prepared to improve accuracy in the
Rubber and are the direct responsibility of Subcommittee D11.23 on Synthetic weighing of these materials. The material blend is prepared by blending a
Rubber. proportional mass of each material in a dry powder blender such as a biconical
Current edition approved May 10, 1999. Published June 1999. Originally blender or vee blender. A mortar and pestle may be used for blending small
published as D 3189 – 73. Last previous edition D 3189 – 94. quantities.
2
Annual Book of ASTM Standards, Vol 04.04.
3
Annual Book of ASTM Standards, Vol 09.01. 5. Sample Preparation
4
Annual Book of ASTM Standards, Vol 05.01.
5
Discontinued—see 1986 Annual Book of ASTM Standards, Vols 09.01 and 5.1 For tests intended for referee purposes obtain and
09.02. prepare the test samples in accordance with Practice D 3896.

1
 D 3189
6. Mixing Procedures 6.2.3 Final Mix:
6.1 The following four mixing procedures are offered: Accu-
Dura- mula-
6.1.1 Test Method A— Internal Mixer for Initial and Final tion, tive,
Mix, min min
6.1.2 Test Method B— Initial Mixer with Final Mill Mix,
6.2.3.1
6.1.3 Test Method C— Mill Mix, and
Adjust the internal mixer to 40 6 5°C (104 6 0
6.1.4 Test Method D— Miniature Internal Mixer Mix. 9°F). Turn off steam and turn on full cooling wa-
ter to the rotors, start the motor at 8.0 rads/s
NOTE 2—The compound may be prepared either on a mill or in an (77 r/min) and raise the ram.
internal mixer or in a miniature internal mixer although slightly different
results may be obtained. 6.2.3.2
NOTE 3—Since the mill handling characteristics of the solution polyb- Charge one half the masterbatch, with all the 0.5 0.5
utadiene rubber are somewhat more difficult than for other polymers; the sulfur and accelerator rolled into this portion of
use of one of the internal mixer procedures is recommended (Test Method the masterbatch before feeding to the mixer.
Add the remaining portion of the masterbatch.
A, B, or D). The mill procedure (Test Method C) may be used provided
Lower the ram.
good carbon black dispersion is obtained.
6.2.3.3
6.2 Test Method A—Internal Mixer for Initial and Final
Allow the batch to mix until a temperature of 2.5 3.0
Mix: 110 6 5°C (230 6 9°F) or a total mixing time of
6.2.1 For general mixing procedure, refer to Practice 3 min is reached, whichever occurs first. Dis-
D 3182. charge the batch. Subtotal Time (min) max.
6.2.2 Mixing Cycle— Initial Mix: 6.2.3.4
Accu- Check the batch mass and record. If it differs
Dura- mula- from the theoretical value by more than 0.5 %,
tion, tive, discard the batch.
min min
6.2.3.5
6.2.2.1
Set with the rolls of a standard laboratory mill 2.0 5.0
Adjust the internal mixer temperature to 0 0 maintained at 40 6 5°C (104 6 9°F) and at 0.8
achieve the discharge conditions outlined in mm (0.032 in.) opening. Pass the rolled stock
6.2.2.5. Close the discharge gate, start the ro- endwise through the mill six times.
tor, at 8.0 rads/s (77 r/min) and raise the ram.
6.2.3.6
6.2.2.2
Open the mill to give a minimum stock thick- 1.0 6.0
Charge one half the rubber, all of the zinc 0.5 0.5 ness of 6 mm (0.25 in.) and pass the stock
oxide, carbon black, oil, stearic acid, and then through the rolls four times, folding it back on
the other one half of the rubber. Lower the ram. itself each time.
6.2.2.3 6.2.3.7 Cut enough sample to allow testing of compound
Allow the batch to mix. 3.0 3.5 viscosity in accordance with Test Method D 1646 or vulcaniz-
6.2.2.4 ing characteristics in accordance with Test Method D 2084, as
Raise the ram and clean the mixer throat and 0.5 4.0 described in 8.2, or both, if these are desired.
the top of the ram. Lower the ram. 6.2.3.8 Set the mill opening to give a finished gage of 2.2
6.2.2.5 mm (0.085 in.). Sheet off the compound from the mill. Cool on
Allow the batch to mix until a temperature of 2.0 6.0
a flat, dry metal surface.
170°C (338°F) or a total mixing time of 6 min is 6.2.3.9 For routine laboratory testing, condition the sheeted
reached, whichever occurs first. Discharge the compound for 1 to 24 h at 23 6 3°C (73.4 6 5.4°F) and a
batch. Subtotal time (min) max.
relative humidity not greater than 55 %. For maximum preci-
6.2.2.6 sion, condition for 1 to 24 h in a closed container to prevent
Check the batch mass and record. If it differs absorption of moisture from the air or in an area controlled at
from the theoretical value by more than 0.5 %, 35 6 5 % relative humidity.
discard the batch.
6.3 Test Method B—Internal Mixer for Initial Mix With
6.2.2.7 Final Mill Mix:
Pass the batch immediately through the stan- 1.0 7.0 6.3.1 For general mixing procedure refer to Practice
dard laboratory mill three times, set at 6.0 mm
(0.25 in.) and 40 6 5°C (104 6 9°F).
D 3182.
6.3.2 Mixing Cycle—Initial Mix:
6.2.2.8 6.3.2.1 Prepare the initial mix in accordance with the
Allow the stock to rest for 1 to 24 h. procedure outlined in 6.2.2.

2
 D 3189
6.3.3 Final Mix: 6.4.2 Mixing Cycle:
Accu- Cu-
Dura- mula- Dura- mula-
tion, tive, tion, tive
min min min Time,
min
6.3.3.1
6.4.2.1
With the roll maintained at 40 6 5°C (104 6 9°F) 0 0
and set at 1.5 mm (0.06 in.) opening, band, on the slow With rolls temperature set at 35 6 5°C and open- 1.5 1.5
roll, the amount of masterbatch based on two times the ing of 0.46 mm band the rubber on the front roll.
formula.
6.4.2.2
6.3.3.2 Add the preblended zinc oxide and stearic acid 2.5 4.0
evenly across the rolls. Make two 3⁄4cuts from each
Add slowly the required amount of sulfur and accel- 1.0 1.0
side.
erator.
NOTE 5—Do not cut the batch while any free ingredient is evident in the
6.3.3.3 bank or on the milling surface.
Make three 3⁄4cuts from each side. 2.0 3.0
6.4.2.3
6.3.3.4 Add a small amount of dry carbon black evenly 10.0 14.0
Cut the batch from the mill, and set the mill-roll open- 2.0 5.0 across the rolls, then using a spatula, wipe some of
ing at 0.8 mm (0.032 in.) and pass the rolled stock end- the oil-carbon black paste on to the mix. Repeat the
wise through the mill six times. sequence of dry black addition followed by the
paste until all the paste has been added. Use a
6.3.3.5 small piece of the mix to wipe out the paste con-
tainer. Continue to add the dry black slowly until
Open the mill to give a minimum stock thickness of 6 1.0 6.0 half the black is added. Increase the mill opening to
mm (0.25 in.) and pass the stock through the rolls four 0.6 mm and continue to add the remaining black in
times, folding it back on itself each time. small amounts. Clean the black out of the mill pan
and add it to the mix.
6.3.3.6 Check the batch mass and record. If it differs from
the theoretical value by more than 0.5 %, discard the batch. 6.4.2.4
Make three 3⁄4 cuts from each side. 1.5 15.5
6.3.3.7 Cut a specimen to allow testing of compound
viscosity in accordance with Test Method D 1646 or vulcaniz- 6.4.2.5
ing characteristics with the oscillating disk cure meter in Add the TBBS and mix until no white spots are 2.0 17.5
visible in the mix. Then slowly add the sulphur
accordance with Test Method D 2084 as described in 8.2, or evenly across the rolls.
both, if these are desired.
6.3.3.8 Set the mill opening to give a finished gage of 2.2 6.4.2.6
Make six successive 3⁄4 cuts from each side. 2.0 19.5
mm (0.085 in.). Sheet off the stock from the mill. Cool on a
flat, dry metal surface. 6.4.2.7
6.3.3.9 For routine laboratory testing, condition the sheeted Cut the batch from the mill. Set the mill opening 2.0 21.5
at 0.8 mm and pass the rolled batch endwise
compound for 1 to 24 h at 23 6 3°C (73.4 6 5.4°F) and a through the the rolls six times.
relative humidity not greater than 55 %. For maximum preci-
sion, condition for 1 to 24 h in a closed container to prevent 6.4.2.8 Sheet the batch to 6 mm thickness and weigh it. If
absorption of moisture from the air or in an area controlled at the weight differs by more than 0.5 % from the theoretical,
35 6 5 % relative humidity. discard it.
6.4.2.9 Cut a specimen to allow testing of compound
NOTE 4—If the amount of one compound based on two times the viscosity in accordance with Test Method D 1646 or vulcaniz-
formula is not enough for the test specimens, another final compound ing characteristics in accordance with Test Method D 2084 as
should be prepared. described in 8.2, or both, if these are desired.
6.4 Test Method C—Mill Procedure: 6.4.2.10 Set the mill opening to give a finished gage of 2.2
6.4.1 For general mixing procedure, refer to Practice mm (0.085 in.). Sheet off the compound from the mill. Cool on
a flat, dry metal surface.
D 3182.
6.4.2.11 For routine laboratory testing, condition the
6.4.1.1 Pre-blend the zinc oxide and stearic acid in a single sheeted compound for 1 to 24 h at 23 + 3°C (73.4 + 5.4°F) and
container. a relative humidity not greater than 55 %. For maximum
6.4.1.2 To simplify the addition of the oil, prepare an precision, condition for 1 to 24 h in a closed container to
oil-carbon black paste as follows: Add the oil to a 100 mL prevent absorption of moisture from the air or in an area
beaker. While stirring the oil with a spatula, slowly add 30 g of controlled at 35 6 5 % relative humidity.
the carbon black until a paste is formed. 6.5 Test Method D—Miniature Internal Mixer (MIM) Pro-
6.4.1.3 Adjust the mill cooling conditions to maintain a cedure:
temperature of 35 6 5°C throughout the mixing operations. 6.5.1 For general mixing procedure, refer to Practice
Adjust the mill openings as necessary to maintain a good D 3182.
rolling bank at the nip of the rolls during the mixing. 6.5.2 Mix with the head temperature of the miniature

3
 D 3189
internal mixer maintained at 60 6 3°C (140 6 5°F) and the 7. Preparation and Testing of Vulcanizates
rotor speed set at 6.3 to 6.6 rad/s (60 to 63 r/min). 7.1 For stress-strain testing, prepare the test sheets and
6.5.3 Prepare the rubber by passing it through a mill one vulcanize them in accordance with Practice D 3182.
time with the temperature set at 40 6 5°C (109 6 9°F) and an 7.1.1 The recommended standard vulcanization times for
opening that would give approximately 5 mm (0.2 in.) thick the mixes prepared by Test Methods A, B and C are 25, 35, and
sheet. Cut the sheet into strips that are approximately 25 mm (1 50 min at 145°C (293°F). The recommended cure time for the
in.) wide. miniature internal mixer compound is 35 min at 145°C
Accu- (293°F).
Dura- mula-
tion, tive,
7.1.2 Condition the cured sheets for 16 to 96 h at a
min min temperature of 236 2°C (73.4 6 3.6°F).
6.5.3.1 NOTE 7—Quality control of rubber production may require testing
Charge the mixing chamber with the rubber strips, 0.0 0.0 within 1 to 6 h to provide close surveillance; however, slightly different
lower the ram, and start the timer. results may be obtained.
6.5.3.2 7.1.3 Prepare the test specimens and obtain the modulus,
Masticate the rubber. 0.5 0.5 tensile, and elongation parameters in accordance with Test
Method D 412.
6.5.3.3 7.2 An alternative to measuring vulcanization characteris-
Raise the ram, add zinc oxide, sulfur, stearic acid, 1.0 1.5
and TBBS that have previously been blended, taking
tics by means of tensile stress measurements on vulcanizates is
care to avoid any loss. the measurement of vulcanization characteristics with an
Ocillating Disk cure meter in accordance with Test Method
6.5.3.4
D 2084, or a Rotorless Cure Meter in accordance with Test
Add portions of the carbon black and oil alternately, 1 2.5
sweep the orifice, and lower the ram.
Method D 5289. These methods will not produce equal results.
7.2.1 The recommended standard Oscillating Disk test con-
6.5.3.5 ditions are 1.7 Hz oscillation frequency; 61° amplitude in
Allow the batch to mix, raising the ram momentarily 6.5 9.0 oscillation, 160°C die temperature, 30 min test time, and no
to sweep down, if necessary.
preheating. The recommended test conditions for the Rotorless
NOTE 6—If only the measurement of cure meter parameters is required, Cure Meter are 1.7 Hz oscillation frequency, 60.5° of arc for
a 5-min mixing cycle may be used reducing the step 6.5.3.5 to 2.5 min. torsional shear cure meters and 60.05 mm for linear shear cure
6.5.3.6 Turn off the motor, raise the ram, remove the mixing meters, 160° C die temperature, 30 min test time, and no
chamber, and discharge the batch. Record the maximum batch preheating. Tolerances for the listed conditions are included in
temperature indicated, if desired. the specified test methods.
6.5.3.7 Pass the batch through a mill at 40 6 5°C (1046 7.2.2 The recommended standard test parameters are: ML,
9°F) and 0.5 mm (0.020 in.) opening once, then twice at 3 mm MH, tsl, t850, and t890.
(0.125 in.) opening. NOTE 8—It is recommended that M H, if applicable, be taken as the
6.5.3.8 Check the batch mass and record. If it differs from torque value at 30 min.
the theoretical value by more than 0.5 %, discard the batch.
6.5.3.9 Cut a specimen for testing vulcanization character- 8. Precision and Bias 6
istics in accordance with Test Method D 2084, as described in 8.1 This precision and bias section has been prepared in
8.2, if required. Condition the specimens for 1 to 24 h at 23 6 accordance with Practice D 4483. Refer to this practice for
3°C (73.4 6 5.4°F) before testing. terminology and other statistical details.
6.5.3.10 If either compound-viscosity or stress-strain testing 8.2 The precision results in this precision and bias section
is required, pass the rolled stock endwise through the mill 6 give an estimate of the precision of the test method with the
times with the mill temperature at 40 6 5°C (104 6 9°F) and materials used in the particular interlaboratory program as
the roll separation of 0.8 mm (0.032 in.). described below. The precision parameters should not be used
6.5.3.11 Cut a specimen to allow testing of compound for acceptance/rejection testing of any group of materials
viscosity in accordance with Test Method D 1646, if required. without documentation that they are applicable to those par-
6.5.3.12 If tensile stress is required, sheet off the compound ticular materials and the specific testing protocols that include
from the mill at a setting to give a finished gage of approxi- these test methods.
mately 2.2 mm (0.085 in.) by passing the folded stock between 8.3 A Type 2, Class III interlaboratory precision program
the mill rolls set at 40 6 5°C (104 6 9°F) four times always was conducted using the Oscillating Disk Cure Meter. Both
in the same direction to obtain the effects of mill direction. repeatability and reproducibility are short term. A period of a
Cool on a flat, dry metal surface. few days separates each of the two day test results. Four
6.5.3.13 For routine laboratory testing, condition the laboratories participated and five materials were used. There-
sheeted compound for 1 to 24 h at 23 6 3°C (73.4 6 5.4°F) fore, p 5 4, q 5 5, and n 5 2. A test result is the value obtained
and a relative humidity not greater than 55 %. For maximum from one determination.
precision, condition for 1 to 24 h in a closed container to
prevent absorption of moisture from the air or in an area 6
Supporting data are available from ASTM Headquarters. Request RR: D11-
controlled at 35 6 5 % relative humidity. 1067.

4
 D 3189
8.4 The five rubbers used were homogeneous samples of 8.6 The precision for these tests on a relative basis may be
different polybutadienes. Compounds were mixed in each expressed as follows:
laboratory banbury on each day using test method A. The test 8.6.1 Repeatability— The repeatability (r) of these tests has
parameters used are described in 7.2. been established as the appropriate value from the table. Two
8.5 The results of the precision calculations are given in single measurements (determinations) that differ by more than
Table 1 with the range of material mean values listed for each the tabulated (r) (expressed as percentage of their mean value)
must be considered suspect, that is, having arisen from
TABLE 1 Type 2 Precision—Vulcanization Parameters Using the different sample populations. Such a decision dictates that
Oscillating Disk Cure MeterA,B appropriate action be taken.
Range of 8.6.2 Reproducibility— The reproducibility (R) of these
Property Sr r (r) SR R (R)
mean values
tests has been established as the appropriate value from the
ML 8.0–10.3 0.33 0.93 10.4 1.14 3.24 36.3
MH 35.2–29.3 1.37 3.89 10.4 3.72 10.5 28.3
table. Two single measurements (determinations) that differ by
ts1 4.4–5.9 0.11 0.31 5.9 0.81 2.3 44.6 more than the tabulated (R) (expressed as percentage of their
t850 9.6–10.6 0.35 1 9.8 0.91 2.57 25.3 mean value) must be considered suspect, that is, having arisen
t890 13.7–15.5 0.35 0.98 6.8 1.44 4.08 28.2
from different sample populations. Such a decision dictates that
A
Units: ML and MH 5 dN · m; ts1, t850, and t890 5 minutes. appropriate action be taken.
B
This is short term precision with p 5 4, q 5 5, and n 5 2.
sr 5 Within laboratory standard deviation. 8.7 Bias—In test method terminology, bias is the difference
r 5 Repeatability in measured units. between an average test value and the reference (true) test
(r) 5 Repeatability in percent.
SR 5 Between laboratory standard deviation. property value. Reference values do not exist for this test
R 5 Reproducibility in measured units. method since the value or level of the test property is
(R) 5 Reproducibility in percent. exclusively defined by the test method. Bias, therefore, cannot
Outliers have been rejected from the tabled data based on the Practice D 4483
procedure. be determined.

test property measured. The mean values were averaged while 9. Keywords
the standard deviations (s, S) were pooled. 9.1 BR; polybutadiene; polymerization; solution

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