Infrared Spectroscopy of Coatings 8.1 Introduction 81 8.2 Principles. 8-1 8.3 Instrumentation 82 Infrared Microscopy *Iaging 84 Data Collection, 83 Separation + Transmission Specea»Atenuated Total Reflectance (ATR) + Infated Photoacoustic Spectroscopy and Douglas S, Kendall Depth Profiling » Other Smpling Methods [National Enforcement 85 Data Interpretation 85 Investigations Center, US. 8.6 Applications. 8-6 Eavionimental Protection Agency References, 87 8.1 Introduction Infrared (IR) spectroscopy is a most useful technique for characterizing coatings, avery cost-effective and efficent means of gathering information. If not the final answer, IR studies can point the way to jon of techniques needed to solve a problem. Ease of sample preparation is one advantage of IR. There are numerous ways of presenting the coating sample tothe infrated spectrometer. The wide variety of sampling accessories or attachments, which can easily be swapped in and out of most spec- twometers, enables the study of liquids and solids under a wide range of conditions. There is large body. of literature on infrared methodology,'= and there ae extensive collections of reference spectra available. Almost all components of coatings can be identified by IR; it is especially useful for polymers. IR spectroscopy can monitor changes, such as drying, curing, and degradation, which occur to coatings Quality control of raw materials and process monitoring during coating synthesis and formulation can be done by IR spectroscopy. Most important to the identification of coatings and the study of their properties isthe skill of the analytical scientist. This factor is often overlooked because the rend in analytical instrumentation in recent years has heen increasing computer control and automation, Even when these systems are at hand, they have little value without a well-trained and experienced analytical scientist behind them. The individual with a coatings problem or application is well advised to seek the services of an experienced specteoscopist. other informs 8.2. Principles ‘The atoms of any molecule are continuously vibrating and rotating. The frequencies ofthese molecular ‘motions are of the same order of magnitude (10" to 10'cycles per second) as those of IR radiation, When the frequency of molecular motion is the same as that of the IR radiation impinging on that 882 Coatings Technology Handbook, Third Edition 95. 20. 5. 0. 78. 70. ca 0. 55. 50. 45. 40. 38. 20. pp $e 4000 35003000 2500 +2000 «1500 -—«1000 Wavenumbers (ene) ‘Transmittance (%) FIGURE.1. The infrared spectrum ofthe alkyd resin and ols from an exterior primer paint. The spectrum can serve as fingerprint of this material, Many ofthe absorption bands are characteristic of particular functional groups and can be used to obtain structural information about the simple. ‘molecule, and when there is a change in dipole moment during that motion, the molecule can absorb the incident radiation. A plot or graph of these absorptions as a function of wavelength or frequency comprises an IR spectrum, AR region extends from about 2 t0 25 yim (5,000 t0 400 em), the most useful range for sis, The most convenient unit for IR wavelengths is microns or micrometers (im, 10 ‘m). Its mote common now to express the IR spectrum in terms of wave numbers, for which the units are reciprocal centimeters (cm). Wave numbers are proportional to frequency and are calculated (in em) from the wavelength in jum by dividing 10,000 by the wavelength. The near-IR region of the spectrum, occurring at higher frequency (wave numbers) and shorter wavelengths than the mid-IR has found considerable use in recent years, particularly in process contzol and in monitoring relatively well: defined materials It is not very useful for identifying complete unknowns and will not be discussed in this chapter, ‘An IR spectrum such as that shown in Figure 8.1 isa plot of the IR radiation transmitted or absorbed by a sample on the y-axis versus wave numbers or wavelength on the x-axis. As no two substances that absorb IR radiation absorb it atthe same frequencies to the same extent, an IR spectrum is a“fingerprint” of a substance useful in differentiating one molecule from another. Moreover, the spectrum of a mixture, excepting certain hydrogen bonding situations or chemical reactions taking place is simply the sum of the spectra of the individual components comprising the mixture. Figure 8.1 shows the IR spectrum of the alkyd resin and oils from an exterior primer paint. In addition to serving as a fingerprint, an IR spectrum can be interpreted in terms of molecular structure, Functional groups have characteristic absorptions. For instance, carbonyl compounds, such as the polyester in Figure 8.1, have a strong absorption near 1700 wave numbers. 8.3 Instrumentation IR spectrometers are most often Fourier transform IR spectrometers (FTIR). They are sensitive and. versatile instruments controlled by a computer. FTIR spectrometers have a high energy throughput and. can produce useful spectra in a matter of seconds. Their wavelength or frequency calibration is accurate Al references in this chapter to IR spectrometers are to FTIR spectrometers.Infrared Spectroscopy of Coatings 83 8.3.1 Infrared Microscopy IR microspectroscopy is an excellent way to analyze small samples or to examine a small region of a coating"! This might help identify the cause of a failure or blemish, for example. IR microscopes combine a microscope with optics suitable for IR radiation with an IR spectrometer. They can be accessories to IR spectrometers, or they can be stand-alone instruments. A means is provided for the visual observation of the sample so that the analyst can correctly position a small sample or select the desired portion from a larger sample. These means could be eyepieces and lenses for visual observation, fr a video camera with suitable optics with images that appear on the monitor of a PC. With some microscopes, the computer can be used to control the microscope, choosing which point, area or line is to be scanned, Either transmission or reflectance spectra are possible. For transmission measurements, the most common problem is excessive sample thickness. The considerable pressures achieved by a diamond cell can reduce many samples to the thickness required for useful spectra, Objective lenses using, the attenuated total reflectance (ATR) technique are also available. Forensic applications, which may require such analyses as the identification of small paint chips, rely heavily on IR microscopy. Many analysts use IR microscopy for most of their solid samples. many areas of chemical analysis is imaging," and this is true in IR spectroscopy. Just a8 cameras and microscopes produce visible images, it is possible to produce images with IR radiation, With visible images, color is often used to distinguish different parts of the image. An IR image has two- dimensional spatial information, as well as spectral information foreach point of the image. By associating different colors with different parts of the spectrum, itis possible to create a visible image that contains information about the IR response of the specimen. For instance, an image showing how a particular ester was distributed across a coating could be produced. Early IR imaging used a microscope with a stage that moved the sample past the IR objective lens. As each point of the sample passed the lens, an IR spectrum would be obtained. The resulting data would be an array of spectra collected on a gridlike pattern over an area of a sample. A newer development is TRarray detectors that can have 256 by 256 or more detectors arrayed together. Each detector in the array can produce a complete spectrum, so a complete image can be produced with simultaneous scanning ‘This greatly reduces the time required to produce an image and introduces the possibility of kinetic experiments, such as observing the surface ofa coating react or change with time. Most imaging detectors are incorporated into IR microscopes although equipment for macroscopic samples i available. Imaging detectors may not collect data over as wide a range of wavelengths as other detectors, so the suitability of the detector for the analytes of interest should be checked. This field is developing rapidly, so the literature and the major manufacturers, such as Digilab, Nicolet, or Perkin Elmer, should be consulted. 8.4 Data Collection 8.4.1 Separation Often, itis possible to analyze a coating with minimal preparation, At other times itis worth the extra effort to separate a coating into its components." The polymers and resins can be separated from the inorganic components, such as pigments and extenders, on the basis of solubility, as in Figure 8.1. The proper solvent must be chosen that can dissolve the organic components, Heating usually increases the solubility ofthe organic components. After dissolution, filtration or centrifugation can be sed to separate the inorganie pigments and fillers from the dissolved polymers or resins. The dissolved components can be prepared for IR analysis by casting a film on a salt plate or an ATR crystal. Because the solvents can be retained in the cast film, itis recommended that the cast film be dried in an oven before the IR spectrum is scanned. The spectrum of the cast film should be checked for the presence of residual solvents ‘The inorganic components can be scanned as potassium bromide (KBr) pellets or mineral oil mulls oF