1、Designation: D3900 05a (Reapproved 2010)D3900 15Standard Test Methods forRubberDetermination of Ethylene Units in Ethylene-Propylene Copolymers (EPM) and in Ethylene-Propylene-Diene Terpolymers (EPDM) by Infrared Spectrometry1This standard is issued under the fixed designation D3900; the number imme
2、diately following the designation indicates the year oforiginal adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. Asuperscript epsilon () indicates an editorial change since the last revision or reapproval.1. Scope1.1 Thes
3、e test methods cover the determination of the proportion of ethylene and propylene units in ethylene-propylenecopolymers (EPM) and ethylene-propylenediene terpolymers (EPDM) over the range from 35 to 85 mass % ethylene. Four testmethods are needed to encompass the variety of commercial polymers that
4、 contain additives or polymerized diene units thatinterfere with the various infrared peaks. Except when interferences are present, all four test methods should give similar results.The test methods appear in the following order:1.1.1 Pressed Film Test Methods:SectionsTest Method AFor EPM and EPDM b
5、etween 35 and 70mass % ethylene9 14Test Method BFor EPM and EPDM between 60 and 85mass % ethylene, except for ethylene/propylene/1,4-hexadiene terpolymers15 19Test Method CFor all EPM and EPDM polymers between 35and 85 mass % ethylene, using near infrared20 241.1.2 Cast Film Test Methods:Test Method
6、 DFor all EPM and EPDM polymers between 35and 85 mass % ethylene, except for ethylene/propylene/1,4-hexadiene terpolymers25 321.2 These test methods are not applicable to oil-extended EPDM unless the oil is first removed in accordance with Test MethodD.1.3 The values stated in SI units are to be reg
7、arded as standard. No other units of measurement are included in this standard.1.4 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibilityof the user of this standard to establish appropriate safety and health practices and dete
8、rmine the applicability of regulatorylimitations prior to use.2. Referenced Documents2.1 ASTM Standards:2D297 Test Methods for Rubber ProductsChemical AnalysisD3568 Test Methods for RubberEvaluation of EPDM (Ethylene Propylene Diene Terpolymers) Including Mixtures With OilD4483 Practice for Evaluati
9、ng Precision for Test Method Standards in the Rubber and Carbon Black Manufacturing IndustriesE168 Practices for General Techniques of Infrared Quantitative Analysis (Withdrawn 2015)33. Summary of Test Methods3.1 Test Method APressed films are measured for their infrared absorbance ratios at 8.65/13
10、.85 m (1156/722 cm1), and masspercent ethylene is read from a calibration obtained from standard polymers.1 These test methods are under the jurisdiction of ASTM Committee D11 on Rubber and are the direct responsibility of Subcommittee D11.11 on Chemical Analysis.Current edition approved June 1, 201
11、0June 1, 2015. Published December 2010July 2015. Originally approved in 1980. Last previous edition approved in 20052010 asD3900 05a.D3900 05a (2010). DOI: 10.1520/D3900-05AR10.10.1520/D3900-15.2 For referencedASTM standards, visit theASTM website, www.astm.org, or contactASTM Customer Service at se
12、rviceastm.org. For Annual Book of ASTM Standardsvolume information, refer to the standards Document Summary page on the ASTM website.3 The last approved version of this historical standard is referenced on www.astm.org.This document is not an ASTM standard and is intended only to provide the user of
13、 an ASTM standard an indication of what changes have been made to the previous version. Becauseit may not be technically possible to adequately depict all changes accurately, ASTM recommends that users consult prior editions as appropriate. In all cases only the current versionof the standard as pub
14、lished by ASTM is to be considered the official document.Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States1NOTE 1Peak typically appears at the wavelength indicated, but peak may shift slightly in its position.3.2 Test Method BThin press
15、ed films are measured for their infrared absorbance ratios at or near 7.25/13.85 m (1379/722cm1), and mass percent ethylene is read from a calibration obtained from standard polymers.3.3 Test Method CPressed films are measured for their infrared absorbance ratios at or near 8.65/2.35 m (1156/4255 cm
16、1)using near infrared, and mass percent ethylene is read from a calibration obtained from standard polymers.3.4 Test Method DUltra-thin cast films on a salt plate are measured for their infrared absorbance ratios at or near 7.25/6.85m (1379/1460 cm1), and mass percent ethylene is read from a calibra
17、tion obtained from standard polymers.4. Significance and Use4.1 These test methods can be used for determining which EPDM polymers are evaluated in the different compounds in TestMethods D3568.4.2 Differences in ethylene sequence distribution cause differences in crystallinity and green strength at
18、the same ethylenecontent. Since these are important variables in EPM and EPDM processability and end-use properties, the ethylene content of therubber should not be used as the sole measurement to determine the suitability of a particular rubber for an intended purpose.5. Interferences5.1 Ethylene/p
19、ropylene/1,4-hexadiene EPDM has an interference at the 7.25-m (1379-cm1) peak and should be measured byTest Method A or C.5.2 Various commercial polymers have interferences due to additives and stabilizers that prevent or hinder the use of the8.65-m (1156-cm1) peak. Test Methods A and C should be ap
20、plied carefully, or Test Methods B and D should be used asdescribed in the procedure.5.3 Extender oil, when present, will interfere with all determinations and must be removed before infrared analysis.6. Apparatus6.1 Hydraulic Press, capable of 200 MPa (29 000 psi) and 150C.6.2 Infrared Spectrophoto
21、meter, double-beam, having a percent transmission specification of 61 %, or better, at full scale,capable of recording a spectrum over the 2.5 to 15-m (4000 to 667-cm1 or 400 000 to 66 700-m1) region for Test Methods A,B, and D. Test Method C requires an instrument capable of recording a spectrum ov
22、er the 2.0 to 15-m (2000 to 667-cm1 or200 000 to 66 700-m1) region. Any spectrophotometer complying with these requirements may be used. The equipment shall beoperated by an experienced analyst according to the manufacturers directions for optimum performance. Recommended practicesfor general techni
23、ques of infrared quantitative analysis are given in Practices E168.6.3 For routine testing, Fourier Transform Infrared (FT-IR) may be used in place of double beam instruments provided thebaseline calculation procedures in the Procedures and Calculation Sections of each method are followed. Sample fi
24、lm temperatureis lower with FT-IR than double beam instruments, and some partly crystalline polymers may respond differently. Calibrationequations (Section 33) may have different mathematical forms with FT-IR.7. Sampling7.1 Take precautions to ensure as representative a sample as possible for spectr
25、al analysis, since infrared absorption is additivein nature and will be influenced by extraneous materials.7.2 Where possible, take the sample from a freshly cut surface to avoid testing of a partially oxidized polymer.8. Precision and Bias48.1 This precision and bias section has been prepared in ac
26、cordance with Practice D4483. Refer to Practice D4483 forterminology and other statistical calculation details.8.2 The precision results in this precision and bias section give an estimate of the precision of these test methods with thematerials (rubbers) used in the particular interlaboratory progr
27、am as described below. The precision parameters should not be usedfor acceptance or rejection testing of any group of materials without documentation that they are applicable to those particularmaterials and the specific testing protocols that include these test methods.8.3 AType 1 (interlaboratory)
28、 precision was evaluated. Both repeatability and reproducibility are short term; a period of a fewdays separates replicate test results.8.4 The precision of these test methods was determined from an interlaboratory study of several materials by severallaboratories on two days as explained below:4 Su
29、pporting data have been filed at ASTM International Headquarters and may be obtained by requesting Research Report RR: D11-1021.D3900 152Test MethodEthyleneRange, %No. ofLaboratoriesNo. ofMaterialsA 4060 6 3A 6576 5 2B 6066 4 2D (NonoilExtended Polymer) 4070 4 4D (Oil-Extended Polymer) 72 3 1A test
30、result is a single determination of percent ethylene.8.5 The results of the precision calculations for repeatability and reproducibility are given in Table 1 for Test Methods A, B,and D.NOTE 2Insufficient data were generated for Test Method C to calculate a precision statement. However, extensive us
31、e of Test Method C within onelaboratory suggests precision levels similar to the other test methods.8.6 The precision of these test methods may be expressed in the format of the following statements, which use an appropriatevalue of r,R, (r), or (R), to be used in decisions about test results. The a
32、ppropriate value is that value of r or R associated with amean level in Table 1 closest to the mean level under consideration at any given time, for any given material, in routine testingoperations.8.7 RepeatabilityThe repeatability, r, of these test methods has been established as the appropriate v
33、alue tabulated in Table1. Two single test results, obtained under normal test method procedures, that differ by more than this tabulated r (for any givenlevel) must be considered as derived from different or nonidentical sample populations.8.8 ReproducibilityThe reproducibility, R, of these test met
34、hods has been established as the appropriate value tabulated inTable 1. Two single test results obtained in two different laboratories, under normal test method procedures, that differ by morethan the tabulated R (for any given level) must be considered to have come from different or nonidentical sa
35、mple populations.8.9 Repeatability and reproducibility expressed as a percent of the mean level, (r) and (R), have equivalent applicationstatements as above for r and R. For the (r) and (R) statements, the difference in the two single test results is expressed as a percentof the arithmetic mean of t
36、he two test results.8.10 Bias:8.10.1 Bias was established with a round-robin test conducted on six EPM standard polymers by the five U.S. EPM/EPDMmanufacturers. Each manufacturer made eight determinations on each of the six standards, using his own infrared method andabsorbance/ethylene calibration
37、chart. Each individual calibration chart had been established with infrared tests of C14-tagged pilotplant polymers or equivalent, with confirming tests such as NMR used where necessary.58.10.2 Ethylene contents of the following ten EPM standards were established via 13C NMR by a consortium of Europ
38、ean andNorth American laboratories.Standard No. Mass Percent Ethylene61 40.12 52.43 58.64 66.85 70.85 Gardner, I. J., Cozewith, C., Ver Strate, G., “Infrared Determination of Composition of Ethylene-Propylene Copolymers,” Rubber Chemistry and Technology, Vol 44,September 1971, pp. 1015 1024.6 Suppor
39、ting data have been filed at ASTM International Headquarters and may be obtained by requesting Research Report RR: D11-1065.TABLE 1 Type 1 PrecisionNOTE 1The midpoint of the range was used to calculate (r) and (R).Test Method EthyleneRange, % Within LaboratoriesA Between LaboratoriesASr r (r) SR R (
40、R)A 40 to 60 0.569 1.61 3.22 0.857 2.43 4.86A 65 to 76 0.471 1.33 1.90 1.74 4.92 7.0B 60 to 66 0.433 1.23 1.95 0.540 1.53 2.43D(Non OE) 40 to 70 0.856 2.42 4.40 2.11 5.97 10.9D(OE) 72 2.12 6.00 8.3 3.55 10.0 13.9A Sr = repeatability, standard deviation, in measurement units.r = repeatability, in mea
41、surement units.(r) = repeatability, (relative) percent.SR = reproducibility, standard deviation, in measurement units.R = reproducibility, in measurement units.(R) = reproducibility, (relative) percent.D3900 1536 78.67 44.88 52.69 69.510 77.58.10.3 The standards were each produced in a commercial pl
42、ant and sizable quantities have been set aside for calibrationpurposes (see 13.2).8.11 The precision of Test Method A was determined utilizing FTIR spectrometers from an interlaboratory study of fivematerials by nine laboratories on two days. The results of the precision calculations for repeatabili
43、ty and reproducibility are givenin Table 2. The FTIR spectrometers utilized were calibrated using the percent ethylene values established by 13C NMR.TEST METHOD APRESSED FILM METHOD USING THE 8.65/13.85-m PEAK RATIO9. Scope9.1 This test method covers the determination of percent ethylene in EPM and
44、EPDM between approximately 35 and 70mass %.9.2 This test method may be used with caution between approximately 60 and 80 mass % ethylene, but is inferior to TestMethod B in precision with many instruments.9.3 Additives in some commercial polymers will cause an additional absorbance on the shoulder o
45、f the 8.65-m (1156-cm1)peak at approximately 8.93 m (1120 cm1), giving difficulty in drawing the baseline. Where this occurs, Test Method B or D mustbe used.9.4 This test method is not intended for oil-extended polymers unless the oil is first removed by extraction.10. Summary of Test Method10.1 Thi
46、s test method makes use of the ratio of the absorbance of methyl groups from propylene units at 8.65 m (1156 cm1)versus the absorbance of methylene sequences from ethylene units at 13.85 m (722 cm1). A series of known EPM polymers isused to prepare a calibration of A8.65 /A13.85 versus mass percent
47、ethylene.11. Reagents and Materials11.1 Purity of ReagentsReagent grade chemicals shall be used in all tests. Unless otherwise indicated, it is intended that allreagents shall conform to the specifications of the Committee on Analytical Reagents of the American Chemical Society, wheresuch specificat
48、ions are available.7 Other grades may be used, provided it is first ascertained that the reagent is of sufficiently highpurity to permit its use without lessening the accuracy of the determination.11.2 Exercise all safety and health precautions while carrying out the subsequent analyses, especially
49、those involving the useof toxic or flammable solvents, or both.11.3 Acetone.11.4 Adhesive Labels.11.5 Flat Steel Plates, 200 by 200 by 1.5 mm (8 by 8 by 0.06 in.).11.6 Polyester Film, uncoated, 0.04 mm (0.0015 in.) thick.11.7 TFE-Fluorocarbon-Coated Stainless Steel or Aluminum Foil.7 Reagent Chemicals, American Chemical Society Specifications, American Chemical Society, Washington, DC. For Suggestions on the testing of reagents not listed bythe American Chemical Society, see Annual Standards for Laboratory Chemicals,
