Designation: D 6645 – 01

Standard Test Method for

Methyl (Comonomer) Content in Polyethylene by Infrared
Spectrophotometry1
This standard is issued under the fixed designation D 6645; 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 E 177 Practice for Use of the Terms Precision and Bias in
1.1 This test method covers the determination of methyl ASTM Test Methods7
groups (that is, comonomer content) in polyethylenes by E 932 Practice for Describing and Measuring Performance
infrared spectrophotometry. The test method is applicable to of Dispersive Infrared Spectrophotometers6
copolymers of ethylene with 1-butene, 1-hexene, or 1-octene E 1421 Practice for Describing and Measuring Performance
having densities above 900 kg/m3. High-pressure low-density of Fourier Transform Infrared (FT-IR) Spectrometers:
polyethylenes (LDPE) and terpolymers are excluded. Level Zero and Level One Tests6
1.2 The values stated in SI units, based on IEEE/ASTM S1- IEEE/ASTM SI-10 Standard for Use of the International
10, are to be regarded as the standard. System of Units (SI): The Modern System (Replaces ASTM
1.3 This standard does not purport to address all of the E 380 and ANSI/IEEE Standard 268-1992)8
safety concerns, if any, associated with its use. It is the 3. Terminology
responsibility of the user of this standard to establish appro-
priate safety and health practices and determine the applica- 3.1 Terminology—The units, symbols, and abbreviations
bility of regulatory limitations prior to use. used in this test method appear in Terminology E 131 or
IEEE/ASTM S1-10.
NOTE 1—There is no similar or equivalent ISO standard. 3.2 comonomer—a-olefin monomer. In this test method,
2. Referenced Documents comonomer refers to 1-butene, 1-hexene, and 1-octene only.
2.1 ASTM Standards: 4. Summary of Test Method
D 792 Test Method for Density and Specific Gravity (Rela- 4.1 The band located between 1377 cm-1 and 1379 cm-1 is
tive Density) of Plastics by Displacement2 due to a deformation vibration of the –CH3 group. Bands at
D 1505 Test Method for Density of Plastics by the Density- approximately 772 cm-1 (branch methylene rocking mode), 895
Gradient Technique2 cm-1 (methyl rocking mode), and 785 cm -1 (branch methylene
D 1898 Practice for Sampling of Plastics3 rocking mode) are characteristic of ethyl (that is, butene
D 2238 Test Method for Absorbance of Polyethylene Due to copolymer), butyl (that is, hexene copolymer), and hexyl (that
methyl Groups at 1378 cm-12 is, octene copolymer) branches, respectively.9
D 3124 Test Method for Vinylidene Unsaturation in Poly- 4.2 This test method determines the methyl (that is,
ethylene by Infrared Spectrophotometry4 comonomer) content of a polyethylene copolymer based on the
D 5576 Practice for Determination of Structural Features in IR absorbance at 1378 cm -1 from a pressed plaque. The
Polyolefins and Polyolefin Copolymers by Infrared Spec- comonomer type has to be known and a calibration curve has
troscopy5 to be available prior to the analysis. If the comonomer is not
E 131 Terminology Relating to Molecular Spectroscopy6 known a priori, the presence of bands at 772 cm-1, 895 cm-1,
E 168 Practice for General Techniques of Infrared Quanti- and 785 cm-1 can be used to identify ethyl (minimum of 1
tative Analysis6 branch per 1000 carbons), butyl (minimum of about 5 branches
per 1000 carbons), and hexyl (minimum of about 5 branches
1
This test method is under the jurisdiction of ASTM Committee D20 on Plastics
per 1000 carbons) branches, respectively. A more sensitive and
and is the direct responsibility of Subcommittee D20.70 on Analytical Methods.
Current edition approved March 10, 2001. Published June 2001.
2 7
Annual Book of ASTM Standards, Vol 08.01. Annual Book of ASTM Standards, Vol 14.02.
3 8
Discontinued; see 1998 Annual Book of ASTM Standards, Vol 08.01. Annual Book of ASTM Standards, Vol 14.04.
4 9
Annual Book of ASTM Standards, Vol 08.02. Blitz, J. P., and McFadden, D. C., “The Characterization of Short Chain
5
Annual Book of ASTM Standards, Vol 08.03. Branching in Polyethylene Using Fourier Transform Infrared Spectroscopy,” J.
6
Annual Book of ASTM Standards, Vol 03.06. Appl. Pol. Sci., 51, 13 (1994).

Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.

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 D 6645 – 01
less ambiguous identification is obtained by C13 NMR spec- 7.1.1 Dispersive Infrared Spectrophotometer, capable of
troscopy. The latter technique is also used as a reference achieving a spectral bandwidth of 4 cm-1 (see Practice E 932).
technique to provide polymer standards for the generation of The instrument should be capable of scale expansion along the
calibration curves. wavenumber axis.
7.1.2 Fourier Transform Infrared Spectrometer, capable of
NOTE 2—For comonomer identification, it is recommended, for maxi-
mum sensitivity, to view the second derivative of the IR spectrum. 4 cm-1 resolution (see Practice E 1421). The instrument should
be capable of scale expansion along the wavenumber axis.
4.3 The method is calibrated by plotting absorbance at 1378 7.2 Compression Molding Press, with platens capable of
cm-1 per unit area of the methylene combination band at 2019 being heated to 180°C.
cm-1 (that is, internal thickness correction approach) or per unit 7.3 Two Metal Plates, 150 by 150 mm or larger, of 0.5-mm
of spectral cross-section (that is, the reciprocal of the product thickness with smooth surfaces.
of plaque thickness and density) versus number of branches per 7.4 Brass Shims, approximately 75 by 75 mm, of 0.3 mm
1000 carbons as determined by C13 NMR spectroscopy. thickness with an aperture in the center at least 25 by 38 mm.
Although both approaches give equivalent results, the one 7.5 Micrometer (optional), with thimble graduations of
using internal thickness correction is recommended in this test 0.001 mm.
method since it is considerably simpler to execute. 7.6 Film Mounts, with apertures at least 6 by 27 mm, to hold
the specimens in the infrared spectrophotometer.
5. Significance and Use
5.1 This method determines the number of branches (that is, 8. Materials
comonomer content) in copolymers of ethylene with 1-butene, 8.1 Polyethylene Terephthalate, Aluminum Foil or Matte
1-hexene or 1-octene. This information can be correlated with Finished Teflon-Fibreglass Sheets.
physical properties such as melting point, density, and stiffness,
all of which depend on the degree of crystallinity of the 9. Hazards
polymer. Differences in the comonomer content thus may have
9.1 Caution must be used during plaque preparation to
a significant effect on the final properties of products made
handle the hot platens with appropriate gloves for hand
from these resins.
protection.
6. Interferences
10. Procedure
6.1 A conformational CH2 wagging absorbance at 1368
10.1 Preparation of Polymer Plaque:
cm-1 overlaps the methyl absorbance at 1378 cm-1, but does not
10.1.1 Preheat the press to about 50°C above the melting
cause significant interference in this test method since its
point of the polymer.
intensity is not significantly affected by the comonomer con-
10.1.2 Place a 0.3-mm thick brass shim on the sheet
tent, but rather by the plaque thickness. The result of not
material chosen (see 8.1) which in turn covers a metal plate.
correcting for this overlap is a positive ordinate intercept for
the calibration curve (see 10.4). Another conformational CH2 NOTE 3—When using aluminum foil, place the dull side next to the
wagging absorbance at 1352 cm-1 does not significantly polymer to give the sample film some texture, thereby reducing fringe
overlap the 1378 cm-1 absorbance. effects in the infrared spectrum.
6.2 The presence of most pigments will interfere with this 10.1.3 Add polymer in sufficient quantity to completely fill
method. the shim aperture during pressing.
6.3 The presence of low molecular weight hydrocarbons 10.1.4 Insert the mold assembly between the press platens
will produce high results in this method due to absorbance by and apply a slight pressure.
their end methyl groups at 1378 cm-1. 10.1.5 Allow the polymer to preheat for about 30 s. Apply
6.4 The secondary antioxidant Irgafos 16810 shows an the full press pressure at a temperature approximately 50°C
absorbance at 768 cm-1 which interferes with the identification above the melting point of the polymer for 1 min or until all
of low levels (that is, typically less than 5 branches per 1000 exudation ceases.
carbons or less) of ethyl branches. 10.1.6 Turn off the heat, turn on the cooling water, and
6.5 Vinylidene groups absorb at 888 cm-1 and thus may allow the polymer to press quench at full pressure until the
interfere with a conclusive identification of a hexene copoly- temperature drops below 50°C (or cool enough to remove the
mer from its 895 cm-1 resonance, depending on the relative mold assembly by hand).
intensities of the two peaks. 10.1.7 Select plaques that are clear for the FTIR analysis. To
avoid interference fringes in the spectrum, the plaque surfaces
7. Apparatus must be slightly dimpled.
7.1 Infrared Spectrophotometer, either double beam or a 10.2 Spectral Acquisition:
Fourier transform (FTIR). 10.2.1 Place the polymer plaque in the infrared spectropho-
tometer.
10.2.2 Set the controls of the infrared spectrophotometer for
quantitative conditions with a good signal to noise ratio and a
10
Trademark of the Ciba Specialty Chemicals Co. spectral resolution (bandwidth) of 4 cm-1. For an FTIR, an

2
 D 6645 – 01
apodization function (Beer-Norton medium and Happ-Genzel NOTE 5—The above recommended “internal thickness correction” ap-
have been found to be appropriate) that gives good quantitation proach has been found to yield equivalent results to the more labor
should be used. intensive approach of measuring thickness (b) to the nearest 0.01 mm and
density (d) of the plaque and graphing A (1378 cm-1) / (b · d) vs. N.
10.2.3 Record the infrared spectrum from 4000 cm-1 to 500 NOTE 6—A wedge compensation or spectral subtraction using a ho-
cm-1. mopolyethylene sample as described in Method D 2238 is not required.
10.3 Spectral Data Reduction:
10.5 Calculations:
10.3.1 Determine the absorbance at a fixed wavenumber
10.5.1 Having determined the thickness corrected absor-
(not necessarily at the apex of the 1378 cm-1 peak) between
bance, use the equation for the appropriate regression line fitted
1378 and 1379 cm-1. A linear baseline is to be set between the
to the calibration points to calculate the number of branches
valleys present at 1400 cm-1 and 1330 cm-1 (see Fig. X1.1 in
(N) per 1000 carbons (see 10.4). Ensure that the value obtained
Appendix X1).
is within the high and low limits of the standards. To convert
10.3.2 Determine the area of the combination band at 2019
to comonomer content, use the following expressions:
cm-1 (see Fig. X1.1 in Appendix X1). The baseline and
integration limits are to be set between the valleys on each side N · Mcom
Wt % 5 100 · (2)
of the peak (that is, typically between 1980 and 2100 cm-1). ~1000 – 2N!
N · M com 1 2 · 28
NOTE 4—Several software packages are available with which macros Wt %
can be written to perform the data reduction automatically and consis-
Mcom
tently. Mol % 5 100 · Wt % 100 – Wt %
10.4 Calibration: Mcom 1 28
10.4.1 For a minimum of five (preferably about ten) poly-
mer standards containing known levels of the comonomer of where:
Mcom = the molecular weight of the a-olefin comonomer.
interest, calculate the ratio of the absorbance (A) at 1378 cm-1
(see 10.3.1) and the area of the combination band at 2019 cm-1 11. Report
(see 10.3.2) and plot: 11.1 Complete identification of material tested including
A (1378 cm-1) / Area (2019 cm-1) vs. Number of branches name, manufacturer, lot number and physical form when
(N) per 1000 carbons. sampled,
A linear regression fit should give a positive ordinate 11.2 Date of test,
intercept (representing the contribution from the CH2 wagging 11.3 Number of methyl groups per 1000 carbons and/or
absorbance at 1368 cm -1 and the –CH3 main chain end groups) comonomer content in wt % or mole % for each sample, and
and an R 2 value of 0.98 or better. According to the Lambert- 11.4 Any sample or spectral anomalies observed during the
Beer Law: measurement.
A ~1378 cm21! / Area ~2019 cm21! 5 a · N 1 b (1)
12. Precision and Bias
where: 12.1 The repeatability relative standard deviation for a
a = slope of the regression line, and butene LLDPE with a comonomer content of 4.1 mol % based
b = ordinate intercept. on 12 analyses over a period of two weeks is 0.9 %.
Depending somewhat on the exact wavenumber at which the 12.2 The reproducibility of this test method is being deter-
absorbance of the 1378 cm-1 peak is measured, the slopes of mined and will be available on or before January 1, 2005.
the regression lines should be close to the following:
13. Keywords
ab(butene copolymers) = 0.009
ah(hexene copolymers) = 0.008 13.1 branching; comonomer; FTIR; infrared spectropho-
ao(octene copolymers) = 0.007 tometry; polyethylene

APPENDIX

(Nonmandatory Information)

X1.1 Fig. X1.1

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 D 6645 – 01

FIG. X1.1 FTIR Spectrum (2200 cm-1 to 1200 cm-1) of a Butene

Copolymer Containing 17 Branches per 1000 Carbons

X1.

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