Polymer Materials Analysis by Infrared Spectroscopy

By Joseph E. Sabol

Joseph E. Sabol Chemical Consultant USA

Introduction Infrared (IR) spectroscopy has been one of the workhorses in the analysis of organic compounds and is quite useful in both qualitative and quantitative analysis of polymeric materials. Modern IR spectroscopy is convenient, straightforward and can: Identify unknown materials Determine the quality or consistency of a sample Monitor production and processing, i.e. degree of crosslinking or crystallinaty Determine the composition of a blended mixture.

Figure 1: The spectra of the gasket (topmost), DuPont Vamac N-123, ethylene acrylic elastomer (middle)and (poly)methyl methacrylate: ethylene oxide: methyl methacrylate (bottom). Vamac N-123 was thebest match in the database.

The utility of IR spectroscopy comes primarily from the fingerprint spectral features that each distinct compound provides. The fingerprint features are due to the various interrelated intramolecular bending and stretching modes. While the a priori deconstruction of an IR spectrum can appear bewildering, this complexity of the unique characteristic spectral features is the basis for identifying the molecular structure of the polymer; the use of correlation charts and reference spectra are essential IR spectroscopy can be applied to the analy is of solids, liquids and gases, although most polymer analysis would be on a solid or liquid. Quantitative analysis often requires the use of empirical calibration curves, because IR absorption generally is non-linear with concentration and absorption signals vary with sample preparation.

Theory of IR Absorpton Molecules absorb IR radiation while undergoing a net change in dipole moment from the vibration or rotation between constituent atoms. When the electron density (charge distribution) of the two atoms is different, the fluctuations in dipole moment, from the vibration or rotation, produce an electric field that can interact with the electric field of the IR radiation, resulting in absorption of the IR radiation. A large polymer molecule has a multitude of localised dipole moments and produces a rich IR spectrum. Intramolecular vibrations are bond stretching, which is a change in the interatomic distance, or bending, which is a change in angle between two bonds. Molecular vibrations can be modeled by a simple harmonic oscillator composed of a spring and two masses undergoing displacement. The quantum mechanical treatment of oscillators, including anharmonic terms are only exactly solvable for the simplest molecules. Reasonable predictions of frequency are possible, but are beyond the scope of this paper. Rotational transitions, which are common in the gas phase, are thwarted by intramolecular interactions, e.g. collisions, resulting in broad, continuous signals in solids and liquids. Because molecular rotation is restricted in solids and liquids, vibrational-rotational transitions do not show the sharp, discrete lines that are found in the gas phase and broad vibrational signals are observed. IR spectra of solids and liquids is therefore primarily correlated with vibrational transitions. IR Spectrum The IR portion of the electromagnetic spectrum has wavelengths l longer than visible lightand ranges from 780nm to 1000m, but it is convenient to express the spectral positions in units that are proportional to energy: the reciprocal of the wavelength 1/l is known as the wavenumber, and the particular units of cm-1, i.e. reciprocal centimeters, are the most common. As an example, the limits of the IR spectrum are 780nm = 0.0000780cm and 1000m = 0.01cm and give the reciprocal (wavenumbers) 12,800cm-1 to 10cm-1. The IR spectrum is further subdivided into the near (12,8004000cm-1), middle (4000-200cm-1) and far (200-10cm-1) regions; the most useful is 4000-670cm-1. The functional group region is 4000-1500cm-1, with spectral features arising from absorption of IR radiation due to the bending or stretching of individual chemical bonds, and the fingerprint region, <1500cm-1, with spectral features arising from absorption of IR radiation due to bending or flexing of the entire molecule (coupling and overtones). IR Instrumentation IR spectra can be recorded by scanning a narrow band of IR radiation having intensity I0 through the polymer sample and comparing the transmitted light intensity I with the incident light. The I/I0 is known as the transmittance and the percent transmittance is %T = (I/I0) x 100. Spectra are commonly shown as ordinate %T plotted as a function of abscissa increasing wavelength (decreasing wavenumber). Decreases (troughs) in the ordinate correspond to regions of the spectrum where the sample absorbs IR radiation, and with use of correlation charts, reveal molecular components. However, spectra can be shown as ordinate absorbance A = log (I0 /I) plotted as a function of wavenumber and increases (peaks) in the ordinate correspond to molecular absorptions.

Most modern IR spectrometers do not use the narrow band scanning, but instead the sample is exposed to broad band IR radiation; a beam-splitter and a moving mirror produce two beams with path lengths that vary periodically to give interference patterns. The Fourier transform is used in data processing and the method is denominated as Fourier transform infrared spectroscopy or FTIR. FTIR, when compared with conventional IR, is usually quicker, has higher resolution, is better for weak absorption signals and computerized signal processing (addition or subtraction of spectra from, e.g. solvents). In addition to using the entire IR spectrum on every scan and averaging the signals, the main difference is simply the way that the data is collected and processed; the resulting spectra arise from the same molecular phenomena: vibrating and interacting molecular dipoles. Not all IR spectra are FTIR spectra, but all FTIR spectra are IR spectra and since most readers would probably be using a contemporary FTIR spectrometer, we retain that for the rest of this article. Polymeric samples are usually analysed either as a thin film or as liquid in a non-absorbing sample holder with a solvent (a solution) or without (neat). If a solvent is used, its spectra must be recorded separately and subtracted from the solution spectra; useful solvents are carbon disulfide or tetrachloroethylene, but many others exist. Sodium chloride windows are often used in liquid cells, but moisture absorption and fogging requires periodic polishing. Solids, as a finely ground powder, can be dispersed a heavy hydrocarbon or fluorocarbon oil and placed between salt plates or mixed with potassium bromide and pressed into a pellet; both of these are known as a mull. In addition to the above sample preparation methods, polymer solids can be analysed by internal reflection; when the incident IR beam is at an angle (to the surface) larger than the critical angle, the radiation is reflected completely at the polymerair surface. The same peaks will appear, as observed in a singlepass film, but the intensities can vary. Other solid-phase sample preparation techniques are used, e.g. attenuated total reflection. IR Spectra and Molecular Structure Correlation charts (Table 1) are available from empirical observations of the frequency range that various molecular components (functional groups) absorb. They are not exact, but a summary of where in the IR spectrum the molecular components will absorb and are a good starting point in identification of a polymer. A few important regions are: Hydrogen stretching, 3700-2700cm-1: Since hydrogen is so light when compared with other atoms, hydrogen does most of the moving and is not affected much by the rest of the molecule. Oxygen hydrogen OH, nitrogenhydrogen NH and carbonhydrogen CH stretching appear at 36503580cm-1, 3500-3300cm-1 and 3300- 2850cm-1, respectively. This also illustrates the fact that increasing the mass of the coupled atom increases the vibrational frequency (the heavier atom is more fixed in space).

Figure 2: Baseline corrected spectra of gasket and Vamac N-123. Abscissa is in units of cm-1.

Triple bond region, 2700-1850cm-1: Only a few functional groups absorb in this region:carbonnitrogen triple and carbon-carbon triple bonds appear at 2250-2225cm-1 and 2260-2190cm-1, respectively. Note that sulfur-hydrogen, phosphorous-hydrogen, and silicon-hydrogen appear at 2600- 2550cm-1, 2440-2350cm-1 and 2260- 2090cm-1, respectively. Double bond region, 1950-1450cm-1: The carbonyl, carbon-oxygen double bond, in ketones, aldehydes, acids, amides and carbonates all appears as a sharp peak at 1700cm-1, while esters, acid chlorides and acid anhydrides absorb at slightly higher frequencies, 1170-1725cm-1. Carbon carbon and carbonnitrogen appear at 1690-1600cm-1. Generally, other features are necessary for conclusive identification. The correlation chart, Table 1, is not complete, but contains many of the functional groups that one encounters in polymer analysisby FTIR. Reference library spectra of thousands of common molecules / polymers are often used to obtain the best fit spectra. However, if the analyte polymer is not in the reference library, an exact fit will not occur. Nevertheless, it can give good information, and when added to some chemical intuition, a reasonable conclusion of the analyte can be made.

R is an aliphatic group. Peak Intensity: S is strong; M is moderate; W is weak; sh is sharp and br is broad.

Example of Polymer Analysis by FTIR: Value Cover Gasket from a Diesel Engine In the gasket spectra (Figure 1), from left to right, the weak, broad signal between 3400- 3000cm-1 could be due to a small amount of amine, specifically the nitrogenhydrogen (NH) bonds. The sharper signals at 2900 and 2800cm-1 are from carbonhydrogen (CH) bonds in both the ethylene and methyl acrylate monomers. The very strong, sharp signal at 1710cm-1 is from the carbonyl carbonoxygen (CO) double bonds in the methyl acrylate` and carboxylic monomer. The two signals at 1650 and 1550cm-1 are curious: the carbonnitrogen (CN) bonds generally appear at 14001300cm-1. Beyond 1600cm-1 the direct assignment becomes difficult, as the signals are combinations and overtones; this fingerprint region is useful primarily for confirmation. Nevertheless, the gasket shows these two peaks, but Vamac N-123 does not. Also, note that the bottom spectra, composed of methyl methacrylate shows signals at 3000 and 2950cm-1, which are different from the methyl acrylate Vamac, and the absence of the 1650 and 1550cm-1 signals. Thus, it is unlikely that the gasket contains methyl methacrylate. The gasket is probably not a pure material and the position and intensity of the signals arise from several distinct molecular sources. One possible solution would be to prepare mixtures of, say, 90/10, 80/20 etc. A component other than Vamac N-123 was not identified, but the differences between the gasket and Vamac N-123 suggest that another component, in addition to Vamac-123 is in the gasket.

Figure 2, shows the gasket and Vamac N-123 with baselines normalised and easier to compare. Note that a good match does exist, except for the broad feature at 3400-3000cm-1 and the 1650 and 1550cm-1 signals. This could be due to the amine cure agent or some other unknown material binder. Based on FTIR spectroscopy, the best match from the spectral database for the gasket is Vamac N123. Notwithstanding, the broad feature and the two unidentified signals cannot guarantee a conclusive identification. Industrial elastomers are usually not pure chemical compounds and are often tailored for specific applications. Additional chemical / physical testing, e.g. resistance to solvents, and use of a larger library could potentially resolve this uncertainty. Conclusion FTIR can provide valuable information about the molecular structure of polymeric materials, including the identification of unknown materials. The FTIR spectra of the polymer sample is recorded and compared with reference library spectra to obtain a best fit. Correlation charts are then used to confirm the various functional groups (molecular components) from the observed absorption peaks. Additional chemical / physical testing is also used as confirmation. Acknowledgment www.specialchem4polymers.com www.chem-consult.com