1、Designation: D 3191 06Standard Test Methods forCarbon Black in SBR (Styrene-Butadiene Rubber)Recipeand Evaluation Procedures1This standard is issued under the fixed designation D 3191; the number immediately following the designation indicates the year oforiginal adoption or, in the case of revision
2、, the year of last revision. A number in parentheses indicates the year of last reapproval. Asuperscript epsilon (e) indicates an editorial change since the last revision or reapproval.1. Scope1.1 These test methods cover the standard materials, testformula, mixing procedure, and test methods for th
3、e evaluationand production control of carbon blacks in styrene butadienerubber (SBR).1.2 The values stated in SI units are to be regarded as thestandard. The values in parentheses are for information only.1.3 This standard does not purport to address all of thesafety concerns, if any, associated wit
4、h its use. It is theresponsibility of the user of this standard to establish appro-priate safety and health practices and determine the applica-bility of regulatory limitations prior to use.2. Referenced Documents2.1 ASTM Standards:2D 412 Test Methods for Vulcanized Rubber and Thermo-plastic Elastom
5、ersTensionD 1646 Test Methods for RubberViscosity, Stress Relax-ation, and Pre-Vulcanization Characteristics (Mooney Vis-cometer)D 1799 Practice for Carbon BlackSampling PackagedShipmentsD 1900 Practice for Carbon BlackSampling Bulk Ship-mentsD 2084 Test Method for Rubber PropertyVulcanizationUsing
6、Oscillating Disk Cure MeterD 3182 Practice for RubberMaterials, Equipment, andProcedures for Mixing Standard Compounds and Prepar-ing Standard Vulcanized SheetsD 3674 Test Method for Carbon Black Relative ExtrucionMass3D 4483 Practice for Evaluating Precision for Test MethodStandards in the Rubber a
7、nd Carbon Black ManufacturingIndustriesD 5289 Test Method for Rubber PropertyVulcanizationUsing Rotorless Cure MetersE 145 Specification for Gravity-Convection And Forced-Ventilation Ovens3. Significance and Use3.1 The major portion of carbon black consumed by therubber industry is used to improve t
8、he physical properties, lifeexpectancy, and utility of rubber products. These test methodsprovide an SBR recipe and directions for evaluating all types ofcarbon black intended for use in rubber products. Otherprocedures are available elsewhere in the ASTM standards forthe evaluation of carbon black
9、itself.3.2 These test methods may be used to characterize carbonblack in terms of specific properties of the standard compound.These test methods are useful for the quality assurance ofcarbon black production. They may also be used for thepreparation of reference compounds, to confirm the day-to-day
10、reliability of testing operations used in the rubber industry, forthe evaluation of experimental compounds, and quality controlof production compounds.1These test methods are under the jurisdiction of ASTM Committee D24 onCarbon Black and are the direct responsibility of Subcommittee D24.71 on Carbo
11、nBlack Testing in Rubber.Current edition approved July 1, 2006. Published July 2006. Originally approvedin 1973. Last previous edition approved in 2002 as D 3191 02.2For referenced ASTM standards, visit the ASTM website, www.astm.org, orcontact ASTM Customer Service at serviceastm.org. For Annual Bo
12、ok of ASTMStandards volume information, refer to the standards Document Summary page onthe ASTM website.3Withdrawn.1Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.4. Standard Test Formula4.1 Standard Formula:Material IRMANo.Quantity,
13、parts bymassSBR-1500 . 100.00Zinc oxideB,C91 3.00SulfurB,C31 1.75Stearic acidB,C21 1.00Carbon black . 50.00TBBSC,D. 1.00TotalBatch factor:E156.75AIRM 91 is available from R. E. Carroll, Inc., 1570 North Olden Ave., Trenton, NJ08638; (800) 2579365. IRM 21 and IRM 31 are available from Akron RubberDev
14、elopment Lab, 2887 Gilchrist Road, Akron, OH 44305; (330) 7946600.BFor the MIM procedure, it is recommended that a blend of compoundingmaterials be prepared to improve accuracy of the weighing of these materials. Thismaterial blend is prepared by blending a proportional mass of each material in adry
15、 powder blender such as a biconical blender or vee blender. A mortar and pestlemay be used for blending small quantities.CFor mill mixes, weigh the rubber and carbon black to the nearest 1.0 g, thesulfur and the accelerator to the nearest 0.02 g, and all of the other compoundingmaterials to the near
16、est 0.1 g. For MIM mixes, weigh the rubber and material blendto the nearest 0.01 g and individual pigments, if used, to the nearest 0.001 g.DTBBS is N-tert-butyl-w-benzothiazolesulfenamide.EFor the mill mixes, a batch factor should be selected to the nearest 0.5 to giveas large a total mass as possi
17、ble that will not exceed 525.0 g. Calculate all partsto the nearest 0.01 part. For MIM mixes, calculate a batch factor to the nearest0.01 that will provide a 75 % loading of the mixing chamber.5. Sampling and Sample Preparation5.1 Samples shall be taken in accordance with PracticeD 1799 or Practice
18、D 1900.5.2 The carbon black shall be conditioned before weighingand mixing by heating in a Type 1B oven, as described inSpecification E 145,for1hat1256 3C. The black shall beplaced in an open vessel of suitable dimensions so that thedepth of black is no more than 10 mm during conditioning. Theblack
19、conditioned as above shall be stored in a closed moisture-proof container until ready for mixing.6. Mixing Procedure6.1 For general mixing procedure refer to Practice D 3182.6.1.1 Mixing shall be done with the mill roll temperaturemaintained at 50 6 5C. The indicated mill openings areapproximate and
20、 should be adjusted to maintain a goodworking bank at the nip of the rolls. The following threemixing procedures are offered:(1) Test Method AMill Mix,(2) Test Method BInternal Mixer, and(3) Test Method CMiniature Internal Mixer.6.1.1.1 Check and record the stock mass. If it differs fromthe theoreti
21、cal value by more than 0.5 %, reject the batch. Fromthis stock, cut enough sample to allow testing of compoundviscosity in accordance with Test Methods D 1646, and curingcharacteristics in accordance with Test Method D 2084,orboth, and extrudability of unvulcanized compounds in accor-dance with Test
22、 Method D 3674, if these are desired.6.2 Mixing Cycle:6.2.1 Test Method AMill Mix:Duration,minAccumula-tive, minSet the mill opening at 1.1 mm (0.045 in.)and band the polymer on the front roll.Make34 cuts every12 min from alternatesides.2.0 2.0Add the sulfur slowly and evenly acrossthe mill at a uni
23、form rate.2.0 4.0Add the stearic acid. Make one34 cutfrom each side after the stearic acid hasbeen incorporated.2.0 6.0Add the carbon black evenly across themill at a uniform rate. When one half theblack is incorporated, open the mill to 1.4mm (0.055 in.) and make one34 cut fromeach side. Add the re
24、mainder of the car-bon black. When all the black has beenincorporated, open the mill to 1.8 mm(0.070 in.) and make one34 cut fromeach side.10.0 16.0NoteDo not cut any stock while freecarbon black is evident in the bank or onthe milling surface. Be certain to returnany pigments that drop through the
25、mill tothe milling stock.Add the zinc oxide and TBBS at the1.8-mm (0.070-in.) setting.3.0 19.0Make three34 cuts from each side andcut the stock from the mill.2.0 21.0Set the rolls at 0.8 mm (0.032 in.). Passthe rolled stock endwise through the millsix times.2.0 23.0Open the mill to give a minimum st
26、ockthickness of 6 mm (0.25 in.) and pass thestock through the rolls four times, foldingit back on itself each time.1.0 24.0Total Time 24.06.2.1.1 Sheet off the stock from the mill at a setting to givea finished gauge of approximately 2.2 mm (0.085 in.). Cool ona flat dry metal surface.6.2.1.2 To pre
27、vent absorption of moisture, condition thesheeted stock for 1 to8hatatemperature of 23 6 3C in aclosed container after cooling unless the relative humidity iscontrolled at 35 6 5 % in accordance with Practice D 3182.6.2.2 Test Method BInternal Mixer:6.2.2.1 BR Banbury: Cool water (not over 16C) roto
28、rs at8.06 rad/s (77 r/min). Start loading when Banbury temperaturerecorder indicates 32C.6.2.2.2 Before mixing the first batch, adjust the internalmixer temperature to achieve the discharge conditions outlinedin the table below. Close the gate.Duration,minAccumula-tive, minRaise ram, add SBR-1500 an
29、d zinc ox-ide, and lower ram.0.75 0.75Raise ram, add all other ingredients ex-cept TBBS, and lower ram.D3191062Raise ram, sweep, lower ram. 1.25 2.0Dump at 3.5 min but not over 71C. 1.5 3.5Total Time 3.56.2.2.3 Mill in accordance with Practice D 3182,6by12mill cold water. (Before using the mill warm
30、 up with a batch ofrubber. Start mill operations when roll surface temperature is32C.)6.2.2.4 Sheet out on the mill, weigh, and check batch mass.Discard if more than 0.5 % different from theoretical mass.Duration,minAccumula-tive, minReturn to mill, set at 1.8 mm (0.070 in.)between rolls, band on mi
31、ll, add TBBS, andmake five34 cuts from each side.2.5 2.5Total Time 2.56.2.2.5 Remove stock from the mill in a sheet and allow torest1honaflat, dry metal surface.6.2.2.6 Weigh 650 g, roll, and pass endwise nine times,without banding through the mill set at 0.5 mm (0.020 in.)between rolls. Start with
32、a surface temperature of 32C.6.2.2.7 Sheet out stock to a thickness of about 2.2 mm(0.085 in.) and cool on a flat, dry metal surface.6.2.2.8 To prevent absorption of moisture, condition thesheeted stock for 1 to8hatatemperature of 23 6 3C in aclosed container after cooling unless the relative humidi
33、ty iscontrolled at 35 6 5 % in accordance with Practice D 3182.Vulcanize and test in accordance with Section 7.6.2.3 Test Method CMiniature Internal Mixer:6.2.3.1 Prepare the rubber by passing it through a mill onetime with the mill temperature at 50 6 5C and a mill openingat 0.51 mm (0.020 in.).Dur
34、ation,minAccumula-tive, minWith the head temperature of the minia-ture internal mixer maintained at 60 6 3Cand the unloaded slow rotor speed at 6.3to 6.6 rad/s (60 to 63 r/min), feed the rub-ber into the mixing chamber and start thetimer as soon as all the rubber is added.Break down the rubber. Whil
35、e the rubberis breaking down, set the powder chute inplace.1.0 1.0Add the sulfur, zinc oxide, stearic acid,and TBBS followed by the carbon black.Quickly insert the ram in the chute andplace a 1-kg mass on the ram.1.0 2.0When the ram positon indicates that thecarbon black has been added, remove thech
36、ute and sweep the remaining carbonblack from the ram and chute cavity intothe mixing chamber.1.0 3.0Allow the compound to mix. 6.0 9.0Total time 9.06.2.3.2 Turn off the motor, raise the ram, remove the mixingchamber, and unload the batch. Record the batch temperature ifdesired.6.2.3.3 With the mill
37、at room temperature, pass the batchthrough the mill set at 0.80 mm (0.032 in.). Fold it on itself andfeed it back through the mill five more times, always keepingthe grain in the same direction and folding it on itself eachtime.6.2.3.4 Check the batch mass and record. Reject the batch ifmore than 60
38、.5 % differ from the theoretical mass.6.2.3.5 For testing of stress-strain, pass the batch throughthe mill to produce a stock thickness of 2.2 mm (0.085 in.).6.2.3.6 For testing of curing characteristics in accordancewith Test Method D 2084, pass the batch through the mill toproduce a minimum stock
39、thickness of 6 mm (0.25 in.).6.2.3.7 To prevent absorption of moisture, condition thesheeted stock for 1 to8hatatemperature of 23 6 3C in aclosed container after cooling unless the relative humidity iscontrolled at 35 6 5 % in accordance with Practice D 3182.Vulcanize and test in accordance with Sec
40、tion 7.7. Preparation and Testing of Vulcanizates7.1 For stress-strain testing, prepare test slabs and vulcanizethem in accordance with Practice D 3182.7.1.1 The recommended standard cure is 50 min at 145C.7.1.2 Condition the cured sheets for 1 to 96 h at a tempera-ture of 23 6 3C.7.1.3 Prepare the
41、test specimens in accordance with PracticeD 3182, and obtain modulus, tensile, and elongation param-eters in accordance with Test Methods D 412. Typically, a testspecimen is prepared using the current Industry ReferenceBlack, for example IRB 7, with each set of mixes and the dataobtained is reported
42、 as a difference from the IRB.7.2 An alternative to measuring stress-strain properties ofvulcanizates is the cure-meter measurement of vulcanizationparameters with an Oscillating Disk cure meter in accordancewith Test Method D 2084 or a Rotorless Cure Meter Test inaccordance with Test Method D 5289.
43、7.2.1 The recommended standard Oscillating Disk test con-ditions are: 1.7 Hz oscillation frequency, 61 amplitude ofoscillation, 160C die temperature, 30-min test time, and nopreheating. The recommended test conditions for the RotorlessCure Meter are: 1.7 Hz oscillation frequency, 60.5 of arc fortors
44、ional shear cure meters, 6 0.05 mm for linear shear curemeters, 160C die temperature, 30-min test time, and nopreheating. Tolerances for the listed conditions are included inthe specified test methods.7.2.2 The recommended standard test parameters are ML,MH,ts1,t8c(50), and t8c(90).8. Precision and
45、Bias48.1 This precision and bias statement has been prepared inaccordance with Practice D 4483. Refer to Practice D 4483 forterminology and other statistical details.8.2 PrecisionThe precision results in this precision andbias section give an estimate of the precision of this testmethod with the mat
46、erials (rubbers, carbon blacks, etc.) used inthe particular interlaboratory program described in 8.3 through8.4.2.3. The precision parameters should not be used foracceptance or rejection testing of any group of materials4Supporting data have been filed at ASTM International Headquarters and maybe o
47、btained by requesting Research Report RR: D24-1030.D3191063without documentation that they are applicable to those par-ticular materials and the specific testing protocols of the testmethod.8.3 Mill MixTest Method AA Type 2 interlaboratoryprecision program was conducted in 1990. Both repeatabilityan
48、d reproducibility represent short-term testing conditions.Seven laboratories tested four carbon blacks (SRBs A-4, B-4,D-4, and F-4) once on each of two different days. Test resultswere obtained in accordance with Test Methods D 412 and areexpressed as differences from IRB 6. A test result is the val
49、ueobtained from a single determination. Acceptable differencevalues were not measured (see Table 1).8.3.1 Repeatability:8.3.1.1 Tensile Stress at 300 % ElongationThe pooledrepeatability of Test Methods D 3191 Method A (using TestMethods D 412 Method A) tensile stress at 300 % elongationhas been established as 0.87 MPa (125 psi). Two single testresults (or determinations) that differ by more than 0.87 MPa(125 psi) must be considered suspect, that is, to have comefrom different sample populations. Such a decision dictates thatsome appropria
