1、Designation: D 6493 05Standard Test Methods forSoftening Point of Hydrocarbon Resins by Automated Ring-and-Ball Apparatus1This standard is issued under the fixed designation D 6493; the number immediately following the designation indicates the year oforiginal adoption or, in the case of revision, t
2、he 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. Scope*1.1 These test methods are intended for determining thesoftening point of hydrocarbon resins and similar mate
3、rials bymeans of an automated ring-and-ball apparatus. Portions aresimilar in technical content to the automated-apparatus ver-sions of Test Methods D 36, E 28, and ISO 4625.1.1.1 The ring-and-ball softening point of a hydrocarbonresin may also be determined with lower precision using themanual ring
4、-and-ball softening point procedure in Test Meth-ods E28.1.2 The values stated in SI units are to be regarded as thestandard. The values given in parentheses are for informationonly.1.3 This standard method does not purport to address all ofthe safety concerns, if any, associated with its use. It is
5、 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:D36 Test Method for Softening Point of Bitumen (Ring-and-Ball Apparatus)E1 Specifica
6、tion for ASTM Liquid-in-Glass ThermometersE28 Test Methods for Softening Point of Resins Derivedfrom Naval Stores by Ring-and-Ball ApparatusE 177 Practice for Use of the Terms Precision and Bias inASTM Test MethodsE 691 Practice for Conducting an Interlaboratory Study toDetermine the Precision of a
7、Test Method2.2 ISO Standard:ISO 4625 Binders for paints and varnishesDeterminationof softening pointRing-and-ball method23. Summary of Test Method3.1 These test methods are for the determination of ahydrocarbon resins softening pointthe temperature at whicha disk of the resin held within a horizonta
8、l ring is forceddownward a distance of 25.4 mm (1.00 in.) under the weight ofa standard steel ball, as the specimen is heated at 5C/min. ina specified liquid bath.4. Significance and Use4.1 For hydrocarbon resins, softening does not take place ata definite temperature.As the temperature rises, these
9、 materialsgradually change from brittle solids or very viscous liquids toless viscous liquids. For this reason, determination of thesoftening point must be made by a fixed, arbitrary, and closelydefined method if the results obtained are to be comparable.5. Sample Preparation5.1 Preparation of Sampl
10、e by the Pour Method: Thisprocedure is suitable for resins that can be heated and pouredwithout adverse effect on the softening point.5.1.1 Select a sample representative of the material to betested. The sample should consist of flakes, pastilles, or brokenlumps. Avoid inclusion of finely divided ma
11、terial or dust.5.1.2 Select a quantity of resin having a volume at leasttwice that necessary to fill the desired number of rings, andmelt it in a clean container, using an oven, hot plate, sand bathor oil bath to prevent local overheating. If necessary, stirslowly, taking care to avoid incorporating
12、 air bubbles in thesample. Melt the sample completely, but do not heat it above atemperature necessary to pour the material readily. The timefrom the beginning of heating to pouring should not exceed 15min.5.1.3 For materials that tend to crack or shrink in the ring oncooling, immediately before fil
13、ling the ring, preheat the ring toapproximately the temperature at which the material is to bepoured. The ring, while being filled, should rest bottom down(see Fig. 1(a) on a suitable metal surface. Pour the sample intothe ring so as to leave an excess on cooling. After cooling aminimum of 30 min.,
14、trim off the excess resin from the top andoutside of the ring. To remove excess resin from the top, cut theexcess off cleanly with a heated knife or spatula, or grasp the1These test methods are under the jurisdiction of ASTM Committee D01 onPaint and Related Coatings, Materials, and Applications and
15、 are the directresponsibility of Subcommittee D01.38 on Hydrocarbon Resins.Current edition approved July 1, 2005. Published August 2005. Originallyapproved in 1999. Last previous edition approved in 1999 as D 6493 99.2Available from American National Standards Institute (ANSI), 25 W. 43rd St.,4th Fl
16、oor, New York, NY 10036.1*A Summary of Changes section appears at the end of this standard.Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.ring in a pair of tongs and draw the top surface quickly andfirmly over the surface of a heated
17、 plate.NOTE 1If the determination is repeated, us a clean container and afresh sample.5.2 Preparation of Sample by the Powder Method: Thisprocedure is suitable for high softening-point materials thatcannot be heated and poured without adverse effects on thesoftening point. See Appendix X1.1, Alterna
18、te Sample Prepa-ration Procedures.5.3 Preparation of Samples Having a Low Softening Point(up to 35C (95F):5.3.1 Place a ring on a piece of aluminum foil. Pour thematerial to be tested into the ring, then place the foil and thefilled ring on dry ice or in a freezer to cool. The material in thering mu
19、st be free of bubbles.5.3.2 After cooling, cut and scrape off any excess materialusing a slightly heated spatula, then slide the ring gently fromthe foil. Place the ring in the supporting apparatus, and performthe softening point determination in accordance with Section12.6. Apparatus6.1 Automated R
20、ing-and-Ball Softening Point Instrument,having a test assembly consisting of: a ring holder, a metalplate, and a cover mounted on two support rods (see Fig. 1(b)and (d), a temperature-measuring device (in accordance withSpecification E1), a heating unit, a heating-rate controller, anda digital tempe
21、rature display.6.2 RingA brass, shouldered ring conforming to thedimensions shown in Fig. 1(a).6.3 BallA steel ball, 9.53 6 0.1 mm (38 in.) in diameter,weighing between 3.45 and 3.55 g.6.4 Ball-Centering Guide (optional), having the dimensionsgiven in Fig. 1(c).6.5 Beaker, 600 mL, borosilicate glass
22、, to hold the bathliquid. ensure that the dimensions will properly fit the heatingunit.6.6 StirrerEither a magnetic stirring motor and a mag-netic stir bar, or a direct-driven agitator with a stirring motor.The dimensions of a stir bar must be such that the bar spinsfreely under the test assembly. T
23、he bath must be stirred at aFIG. 1 Shouldered Ring, Ring Holder, Ball-Centering Guide, and Assembly of ApparatusD6493052speed sufficient to ensure uniform temperature distributionwithout causing significant sideways displacement of the resinas it sags below the ring.7. Reagents and Materials7.1 Bath
24、 Liquids:7.1.1 Distilled or Deionized Water, Freshly BoiledForsoftening points between 35C (95F) and 80C (176F).7.1.1.1 Use distilled or deionized water that has been cooledto at least 27C (81F) below the anticipated softening point,but in no case lower than 5C (41F).7.1.2 USP GlycerinFor softening
25、points between 80C(176F) and 150C (302F). Repeated use of glycerin (overabout four heating cycles) may affect results. Open storage ofglycerin can increase the moisture content, which may affectresults. Replace with fresh glycerin if any change in appear-ance or viscosity is noted. Use fresh glyceri
26、n for referee work.WarningGlycerin must not be used for softening pointsgreater than 150C (302F) due to the 160C (320F) flashpoint of glycerin.7.1.3 Silicone Oil (Polydimethylsiloxane)For softeningpoints above 80C (176F). The oil must have a temperaturerange of 60 to 200C+ (140 to 392F+), remain cle
27、ar through-out the temperature range, have no apparent effect or reactivitywith the test specimen, remain free of moisture, and maintaina relatively uniform viscosity and stirring rate within thetemperature range.3NOTE 2Replace with fresh silicone oil if any change in appearance isnoted. Do not use
28、silicone oil that contains any gels; gels are an indicatorthat degradation has occurred.7.1.4 Ethylene GlycolFor softening points up to 35C(95F).7.1.4.1 Prepare a fresh 50/50 (volume/volume) mixture ofdistilled water and ethylene glycol prior to softening pointdetermination. Alternatively, for softe
29、ning points between 0Cand 35C, a 50/50 (v/v) mixture of glycerin and water may beused.8. Calibration8.1 The calibration of any automated ring and ball softeningpoint apparatus must be performed on a regular basis, sinceaccurate temperature control is required. Follow the manufac-turers instructions
30、for calibration of the instrument.9. Procedure for Materials Having a Softening PointBetween 35C (95F) and 80C (176F)9.1 Add a stir bar or stirrer to the 600-mL beaker. Addapproximately 500 mL of water, conforming to the require-ments in 7.1.1. Ensure that the beaker is properly positioned onthe hea
31、ter in the test unit. Place the prepared sample rings inthe test assembly. Place a ball-centering guide and ball on topof each sample ring. Place the test assembly in the beaker.Place the temperature-measuring device in the opening in thecover of the test assembly. Verify that the control unit is se
32、t forthe correct bath liquid.9.2 Heat the bath so that the temperature of the water israised uniformly at a rate of 5C (10F)/min. Protect the bathfrom drafts, using shields if necessary. Reject any test in whichthe rate of temperature rise does not fall within these limits.The test is complete when
33、the light beam has been interruptedby the falling ball and material.NOTE 3Rigid adherence to the prescribed rate of heating is absolutelyessential for reproducibility of results.9.3 Record as the softening point the temperature displayedon the unit after the light beam has been interrupted by thefal
34、ling ball and material.9.4 Start the cooling process in the instrument. Remove thetemperature measuring device from the test insert, then removethe test insert from the beakers. Thoroughly clean the testinsert, ball, and ring in a suitable solvent.10. Procedure for Materials Having Softening PointsB
35、etween 80C (176F) and 150C (302F)10.1 Use the same procedure as described in Section 9,except fill the bath with glycerin or silicone oil.NOTE 4For materials softening around 80C (176F) report the bathliquid used, since a glycerin or silicone oil bath will yield a slightly higherresult than a water
36、bath.11. Procedure for Materials Having Softening PointsAbove 150C (302F)11.1 Use the same procedure as described in Section 9,except fill the bath with silicone oil (see Note 2).12. Procedure for Materials Having Softening PointsBelow 35C (95F)12.1 Additional Apparatus:12.1.1 Isopropyl Alcohol Dry
37、Ice Bath.12.2 Procedure:12.2.1 Cool the beaker containing the liquid bath, describedin 7.1.4.1, to 25C (13F) in an isopropyl alcohol/dry icebath.12.2.2 Use the same procedure as in Section 9 except for thebath liquid, and begin heating as directed once the testspecimen in the ring has been placed in
38、 the bath.13. Report13.1 Report the softening point to the nearest 1C.13.2 Report the bath liquid used in the test.14. Precision and Bias314.1 An interlaboratory study of the ring-and-ball softeningpoint of three hydrocarbon resins was run in 1998 by 23laboratories. The design of the study, similar
39、to that of PracticeE 691, and an analysis of the data are given inASTM ResearchReport No. D01-1113. The precision values given for ring-and-ball softening point of hydrocarbon resins are for the compari-son of two test results (single determinations).14.1.1 For a material having a 70C ring-and-ball
40、softeningpoint, run in a water bath:14.1.1.1 Repeatability Limit 95 % (within laboratory): Thedifference between two results obtained by the same operator3Supporting data are available from ASTM International Headquarters. RequestRR:D011113.D6493053with the same apparatus on identical test material
41、shall, at the95 % confidence level, not exceed 0.7C.14.1.1.2 Reproducibility Limit 95 % (between laboratories):The difference between two results obtained by differentoperators with different apparatus on identical test materialshall, at 95 % confidence level, not exceed 3.9C.14.1.2 For a material h
42、aving a 100 to 135C ring-and-ballsoftening point, run in a glycerin or silicon oil bath:Repeatability Limit 95 % (within laboratory) = 1.8C.Reproducibility Limit 95 % (between laboratories) = 4.6C.14.2 These terms (repeatability limit and reproducibilitylimit) are used as specified in Practice E 177
43、. The respectivestandard deviations among test results, related to the abovenumbers by the factor 2.8, are as follows:14.2.1 For a material having a 70C ring-and-ball softeningpoint, run in a water bath:Repeatability Standard Deviation = 0.3C.Reproducibility Standard Deviation = 1.4C.14.2.2 For a ma
44、terial having a 100 to 135C ring-and-ballsoftening point, run in a glycerin or silicone oil bath:Repeatability Standard Deviation = 0.7C.Reproducibility Standard Deviation = 1.7C.14.3 BiasSince there is no accepted reference material,method or laboratory for determining the bias for the procedurein
45、these test methods for measuring the ring-and-ball softeningpoint, no statement on bias can be made.15. Keywords15.1 hydrocarbon resin; ring and ball; softening pointAPPENDIX(Nonmandatory Information)X1. ALTERNATIVE SAMPLE PREPARATION PROCEDUREX1.1 Preparation of Sample by the Powder Method:X1.1.1 T
46、his sample preparation procedure is suitable formaterials that cannot be melted and poured without altering thesoftening point.X1.1.2 ApparatusFor the powder method of samplepreparation the following additional apparatus is required:X1.1.2.1 RingAs an alternative to the brass ring conform-ing to the
47、 dimensions shown in Fig. 1(a); a ring made of steelmay be used to minimize the possibility of its deformationduring the compacting operation.X1.1.2.2 Ring Support and PestleAsteel pestle and a ringsupport consisting of: sleeve, knock-out-button, ring support,and cup-shaped “mortar,” conforming to t
48、he dimensions shownin Fig. X1.1.X1.1.2.3 PressA hydraulic press or any other suitablepress capable of maintaining sustained pressures up to 55 MPa(8000 psi).X1.1.3 Procedure:X1.1.3.1 Select a sample as described in 5.1.1 and break upthe pieces until there are no particles larger than 3 mm (18 in.).M
49、ix the material thoroughly, and quarter down until a suitablequantity (approximately 50 to 75 g) is obtained for powdering.X1.1.3.2 Pulverize the quartered sample in a porcelainmortar or by other suitable means, and screen through a No. 50sieve. Immediately use the material passing the sieve forpreparation of the specimen.X1.1.3.3 Assemble a ring and the ring support, as shown inFig. X1.1. Ensure that the ring is properly centered and seatedin the cut-out section of the sleeve.X1.1.3.4 Pour the pulv
