Designation: D5576 − 00 (Reapproved 2013)

Standard Practice for

Determination of Structural Features in Polyolefins and
Polyolefin Copolymers by Infrared Spectrophotometry (FT-
IR)1
This standard is issued under the fixed designation D5576; 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 (´) indicates an editorial change since the last revision or reapproval.

1. Scope* Content of Ethylene-Vinyl Acetate (EVA) Copolymers by

1.1 This practice covers infrared procedures for determining Fourier Transform Infrared Spectroscopy (FT-IR)
the molecular structural features in polyolefins and polyolefin D6248 Test Method for Vinyl and Trans Unsaturation in
copolymers. The structural features of primary concern are the Polyethylene by Infrared Spectrophotometry
types and numbers of branches. Although this practice centers E131 Terminology Relating to Molecular Spectroscopy
its attention on polyolefins and polyolefin copolymers, the E168 Practices for General Techniques of Infrared Quanti-
techniques, with proper modification, can be used for some tative Analysis
other polymers as well. E932 Practice for Describing and Measuring Performance of
NOTE 1—Quantitative determinations require either an internal or an Dispersive Infrared Spectrometers
external evaluation of sample thickness. ASTM test methods available for E1421 Practice for Describing and Measuring Performance
specific features are listed in Tables 1 and 2. of Fourier Transform Mid-Infrared (FT-MIR) Spectrom-
1.2 This standard does not purport to address all of the eters: Level Zero and Level One Tests
safety concerns, if any, associated with its use. It is the IEEE/ASTM SI-10 Standard for Use of the International
responsibility of the user of this standard to establish appro- System of Units (SI): The Modern System
priate safety and health practices and to determine the
3. Terminology
applicability of the regulatory limitations prior to use.
3.1 Definitions—For definitions of plastics terms used in
NOTE 2—There is no known ISO equivalent to this standard.
this practice see Terminology D883 and D1600.
2. Referenced Documents 3.2 Units, symbols and abbreviations used in this practice
2.1 ASTM Standards: 2 appear in Terminology E131 or IEEE/ASTM SI-10.
D883 Terminology Relating to Plastics 4. Summary of Practice
D1505 Test Method for Density of Plastics by the Density-
Gradient Technique 4.1 Infrared absorption bands suitable for quantitative
D1600 Terminology for Abbreviated Terms Relating to Plas- analysis by FT-IR are listed in Tables 1 and 2. These are only
tics typical bands and are not to be construed as exhaustive.
D2238 Test Methods for Absorbance of Polyethylene Due to 4.2 For quantitative determinations, sample specimen thick-
Methyl Groups at 1378 cm−1 ness is measured internally at some band representing the basic
D3124 Test Method for Vinylidene Unsaturation in Polyeth- chain structure, such as 2019 cm–1 for polyethylene, or
ylene by Infrared Spectrophotometry externally using a micrometer (see Tables 1 and 2 for ASTM
D3594 Test Method for Copolymerized Ethyl Acrylate In test methods).
Ethylene-Ethyl Acrylate Copolymers NOTE 3—Warning: Molding can cause carbonyl formation due to
D5594 Test Method for Determination of the Vinyl Acetate oxidation. This should be checked in the 1700 to 1750 cm–1 range.

5. Significance and Use

1
This practice is under the jurisdiction of ASTM Committee D20 on Plastics and
is the direct responsibility of Subcommittee D20.70 on Analytical Methods.
5.1 The structural features expressed by these determina-
Current edition approved April 1, 2013. Published April 2013. Originally tions affect the ultimate polymeric properties and are useful in
approved in 1994. Last previous edition approved in 2006 as D5576 - 00(2006). showing correlations with many performance properties.
DOI: 10.1520/D5576-00R13.
2
For referenced ASTM standards, visit the ASTM website, www.astm.org, or 6. Apparatus
contact ASTM Customer Service at [email protected]. For Annual Book of ASTM
Standards volume information, refer to the standard’s Document Summary page on 6.1 Infrared Spectrophotometer, either double beam or a
the ASTM website. Fourier transform (FT-IR).

*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

1
 D5576 − 00 (2013)
TABLE 1 Polyolefin Structural Features Determined by FT-IR 9.1.1.1 Control the hot plate temperature at 100 6 10°C
Structure
Absorption Band,
ASTM Test Method
above the melting temperature of the polymer.
cm–1 9.1.1.2 Place a portion of the sample on a microscope slide
Methyl group 1378 D2238 on the hot plate.
(polyethylene)
Methyl group (eth-prop 1380 9.1.1.3 Cover the sample with another slide and press with
copol) a wooden pestle. Use firm circular motions to press a uniform
Pendant methyl 935 film.
Terminal vinyl 908 D6248
Trans-vinylene 965 D6248 9.1.1.4 To quench the pressed polymer film, dip the two
Vinylidene 888 D3124 slides carefully into a beaker of cold water. Remove the film
and blot dry.
9.1.2 Procedure B:
TABLE 2 Structural Features in Polyolefin Copolymer Determined 9.1.2.1 Preheat the press to about 50°C above the melting
by FT-IR
point of the polymer.
Structure Absorption Band, cm–1 ASTM Test Method
9.1.2.2 Place a brass shim on the sheet material chosen (see
Vinyl acetate 609 D5594 7.1) that, in turn, covers a metal plate.
1020 D5594
3270 D5594 9.1.2.3 Add polymer in sufficient quantity to completely fill
Styrene 770–700 the shim aperture during pressing.
1600–1500
Ethyl acrylate 1640–1730
9.1.2.4 Cover with another piece of sheet (see 7.1) and
862 D3594 another metal plate.
Ethylene acrylate 1280–1200 9.1.2.5 Insert the mold assembly between the press platens
1640–1625
and apply a slight pressure.
9.1.2.6 Allow the sample to preheat for about 30 s. Apply
6.1.1 Double-beam infrared spectrophotometer capable of a the full press pressure at a temperature approximately 50°C
4 cm-1 spectral resolution as defined in Practice E932. The above the melting point of the polymer for 1 min or until all
instrument should be capable of scale expansion along the exudation ceases.
wavelength axis. 9.1.2.7 Turn off the heat, turn on the cooling water, and
6.1.2 Fourier Transform Infrared Spectrometer, capable of 4 allow the sample to press quench at full pressure until the
cm–1 resolution. The instrument should be capable of scale temperature drops below 50°C (or cool enough to remove the
expansion along the wavelength axis. Also, see Practice E1421 mold assembly by hand).
for testing procedures. 9.1.2.8 Release the pressure and remove the sample.
9.1.2.9 Select plaques that are clear and of uniform thick-
6.2 Hot Plate. ness for the FT-IR analysis. To avoid interference fringes in the
6.3 Microscope Slides. spectrum, the plaque/film surfaces must be slightly dimpled.
6.4 Compression-Molding Press, capable of 200°C. 9.2 Spectral Measurements:
6.5 Metal Plates, two, 150 by 150 mm or larger, of 0.5–mm 9.2.1 Place the sample in the infrared spectrophotometer.
thickness with smooth surfaces. 9.2.2 Set the controls of the infrared spectrophotometer for
quantitative conditions with a good signal to noise ratio and
6.6 Brass Shims, approximately 75 by 75 mm, of 0.5-mm satisfactory repeatability. For a FT-IR, a spectral resolution of
thickness with an aperture in the center at least 25 by 38 mm. 4 cm–1 and an apodization function (Beer-Norton medium and
6.7 Micrometer (optional), with thimble graduations of Happ-Genzel have been found to be appropriate) that gives
0.001 mm. good quantitation should be used.
6.8 Film Mounts, with apertures at least 6 by 27 mm, to hold 9.2.3 Record the infrared spectrum from 4000 to 500 cm–1.
the specimens in the infrared spectrophotometer. 9.2.4 Determine which structural feature(s) are present and
select the appropriate ASTM method for quantitative determi-
7. Materials nation.
7.1 Polyethylene Terephthalate, Aluminum or Matte Fin-
ished Teflon-Fiberglass Sheets. 10. Calculation

8. Hazards 10.1 If no standard method is available and an estimate of

the concentration of the feature of interest is sought, the
8.1 Wear gloves when plaques are prepared using a heated approach in 10.1.1-10.1.3 is suggested.
press. 10.1.1 Determine the thickness of the plaque or, preferably,
8.2 The optical bench of the FT-IR spectrometer contains a its spectral cross-section, b, in cm2/g, by measuring the
laser. To avoid eye injury, do not look directly into the laser thickness and density or alternatively the mass and surface area
beam. of a uniformly thick portion of the plaque
10.1.2 Measure the absorbance of the peak of interest.
9. Procedure Choose a baseline between valleys on either side of the peak in
9.1 Sample Preparation: a manner to produce the most accurate and repeatable repre-
9.1.1 Procedure A: sentation of the actual background absorbance

2
 D5576 − 00 (2013)
10.1.3 Calculate the concentration, c, of the feature using 11.1.2 Date of test, and
either the Beer-Lambert Law (A = a · b · c) with the appropri- 11.1.3 Any sample or spectral anomalies observed during
ate molar absorptivity, a, or an appropriate calibration curve. If the measurement.
a calibration curve is used, it should have a minimum of 5 data
points, and the unknown should be within the high and low 12. Keywords
limits of the standards.
12.1 copolymers; FT-IR; infrared spectrophotometry; poly-
11. Report ethylene; structural features
11.1 Report the following information:
11.1.1 Complete identification of material tested including
name, manufacturer, lot number and physical form when
sampled,

SUMMARY OF CHANGES

Committee D20 has identified the location of selected changes to this standard since the last issue
(D5576 - 00(2006)) that may impact the use of this standard. (April 1, 2013)

(1) Reapproved without change.

ASTM International takes no position respecting the validity of any patent rights asserted in connection with any item mentioned
in this standard. Users of this standard are expressly advised that determination of the validity of any such patent rights, and the risk
of infringement of such rights, are entirely their own responsibility.

This standard is subject to revision at any time by the responsible technical committee and must be reviewed every five years and
if not revised, either reapproved or withdrawn. Your comments are invited either for revision of this standard or for additional standards
and should be addressed to ASTM International Headquarters. Your comments will receive careful consideration at a meeting of the
responsible technical committee, which you may attend. If you feel that your comments have not received a fair hearing you should
make your views known to the ASTM Committee on Standards, at the address shown below.

This standard is copyrighted by ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959,
United States. Individual reprints (single or multiple copies) of this standard may be obtained by contacting ASTM at the above
address or at 610-832-9585 (phone), 610-832-9555 (fax), or [email protected] (e-mail); or through the ASTM website
(www.astm.org). Permission rights to photocopy the standard may also be secured from the ASTM website (www.astm.org/
COPYRIGHT/).