Analysis of multi-layer

polymer films
Polymer multi-layer films are used in a variety of industries. It is
important both to the manufacturers of polymer films and to the
industries using these films that the quality and composition be strictly
controlled. The confocal analysis and high spatial resolution of Raman
microscopy make this technique ideal for identifying the source and
identity of defects and inclusions in polymer films.

Paulette Guillory, Tim Deschaines and Pat Henson

Thermo Fisher Scientific, Madison, WI USA

Polymer multi-layer films are used in a variety of industries. In Experimental

food packaging, for example, polymer laminates are used not only For this particular application, the Thermo Scientific Nicolet™
to protect the food, but also to retain aroma and flavors, and to Almega™ XR dispersive Raman spectrometer was used to analyze the
extend shelf life. Multi-layer films are produced using co-extrusion layers of a polymer multi-layer film. The Thermo Scientific OMNIC™
and lamination techniques. Some of the problems that can occur software suite provided the analytical tools used to estimate film
during film manufacture include the introduction of defect thickness and composition.
particles and separation of the layers. Current analytical methods
used to examine the materials during and after production include Confocal analysis
NMR, DSC and FT-IR. Vibrational spectroscopy is a valuable The confocal design of most Raman spectrometers makes it possible to
addition to these techniques because it provides definitive target individual layers in a multi-layered sample. The pinhole aperture
molecular information. Raman spectroscopy is complementary to at the entrance to the spectrograph allows only the Raman scatter
FT-IR and offers advantages that include higher spatial resolution from the focal point of the objective to reach the detector (Fig. 1).
and easier sample preparation. By changing the position of the microscope stage in the vertical
Dispersive Raman spectroscopy offers many advantages over direction, confocal analysis can be used for depth profiling and can
other techniques such as FT-Raman. In comparison with commercial permit the analysis of individual layers of a sample while requiring little
FT-Raman microscopes which have a typical resolution less than 5 μm, or no sample preparation. This technique is very effective for rapid
dispersive Raman spectroscopy uses visible (400 – 785 nm) lasers for identification of sample layers.
sample excitation which permits higher spatial resolution (better than
one micron). In addition, Raman emission is proportional to 1/λ4, Visible microscopy
offering much greater sensitivity. Raman spectroscopy is sensitive The Raman microscope is a powerful research microscope with
to both chemical and physical properties and its unique selection advanced viewing capabilities that include brightfield and darkfield
rules generate a molecular fingerprint that is well suited to material illumination, visual polarization and differential interference contrast
identification. (DIC). DIC is useful for observing multi-layer films as it improves

38 APRIL 2009 | VOLUME 12 | NUMBER 4 ISSN:1369 7021 © Elsevier Ltd 2009 Open access under CC BY-NC-ND license.
 Analysis of multi-layer polymer films APPLICATION

Depth profile analysis

The depth profile line maps were the easiest to collect. The film was
simply immobilized on a slide and the depth profile map collected
using a precision motorized stage with a Z-axis controller. The stage
was moved in 1 μm steps and resolution of better than 2 μm was
observed.

Results
Fig. 1 Confocal analysis. The pinhole aperture at the focal plane of the
microscope permits only the Raman scatter originating from the focal point of Initial depth profile observations of the sample revealed the presence of
the objective to fall on the detector. (a) the detector collects Raman scatter six layers. Some of the layers were tens of microns thick, while others
from the top sample layer; (b) after raising the sampling stage, the detector were much thinner. At the interfaces between the thinnest layers
now collects Raman scatter from the middle sample layer; (c) the detector
collects Raman scatter from the bottom layer. (1 – 3 microns) it was difficult to resolve the spectra of the individual
layers. A line map was also constructed across a cross-section of the
the contrast between different layers and helps to define the layer sample.
boundaries. By rotating a Nomarski prism in the DIC optics, the
changes in the light interference result in pseudo three-dimensional Analysis of layer composition and thickness
images, giving rise to differing regions of color in the sample. In a Layer composition and thickness can be estimated from both the
polymer multi-layer material, this allows the user to selectively analyze cross-section map and from the confocal depth profile of the sample.
different layers in a cross-section of the sample. When samples are mapped using sufficiently small steps, layers of the
order of 500 nm can be detected. The sample was placed cut end up
Sample preparation on a reflective glass slide and analyzed using a line map across the
Cross-sectional analysis sample.
Most multi-layer samples are prepared for microscopic analysis by In order to use a line map to calculate the thicknesses of the
immobilizing the film in epoxy followed by carefully microtoming into constituent layers of a multi-layer sample, it is convenient to select a
micrometer-thin slices. This is necessary for an absorption technique spectral feature that is unique to a specific layer and calculate a profile
such as infrared spectroscopy, in order to prevent over-saturation of of this feature across the line map.
the bands. However since Raman is an emission technique, sample The composition of the six layers was identified by using spectral
thickness is not a critical concern. The microtome slices can be much search to compare the spectra from the layers with those in the
thicker, since only the cross-sectioned end will be analyzed. Samples Thermo Scientific high resolution Raman polymer library. The
can also be simply cross-sectioned, placed cut side up on a glass slide, calculated results are shown in Table 1 and are compared with data
and immobilized using a small piece of double-sided adhesive tape or showing the actual thickness and composition of the sample.
putty. For this application the microscope was focused on the sample The calculated values match very well with the reported values and
edge and a line map constructed. the results were comparable with those obtained using differential
scanning calorimetry (DSC), but took less time to obtain because
Table 1: Multi-layer polymer sample: thickness and
composition of the layers – experimental and reported Raman microscopy is a single technique analysis. The spectral matches
results could have been enhanced by building a specific library against which
Experimental Results Reported to search the data, using spectra collected from the specific polymer
Layer Thickness Composition Thickness Composition formulations in use.
LLDPE, linear
1 1.5 mils (40 μm) Polyethylene 1.61 mil (40.9 μm) low density
polyethylene Conclusion
Polyethylene/ Dispersive Raman microscopy is an excellent technique for the analysis
2 0.1 mils (3 μm) vinyl acetate 0.08 mil (2.03 μm) Polyethylene 1 of multi-thin-layer polymer materials. The spatial resolution of
copolymer
Ethylene vinyl dispersive Raman spectrometers enables the analysis and detection of
3 0.2 mils (7 μm) Vinyl OH 0.27 mil (6.86 μm) alcohol with ~48 layers less than one micron in thickness. The confocal optical design
mole % ethylene
Nylon 6 with a
allows for quick identification of the layers, and the excellent spatial
4 0.7 mils (20 μm) Nylon 0.79 mil (20.1 μm) small amount of resolution in the x, y dimensions permits a more rigorous examination
nylon 6,6
of the material by cross-sectioning. Although not demonstrated in this
Ethylene alpha-
5 0.1 mils (3 μm) Polyethylene 0.09 mil (2.29 μm) article, dispersive Raman microscopy is also ideal for the analysis of
olefin copolymer
6 0.2 mils (5 μm) Polyester 0.14 mil (3.56 μm) Polyester defects and intrusions in the film.

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