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APPLICATION NOTE AP0020712

Noncontact, Real-Time Detection and Analysis of Silicone Films on Surfaces
Abstract
Silicone is a broadly used versatile material. Applications include elastomers, adhesives, seals and release coatings (such as mold release agents). However, in many situations silicone coatings or residues need to be monitored so that they can be repaired or removed. What is needed is a way to detect thin silicone films in a fast efficient manner without contacting the surface. Mid infrared spectroscopy, specifically using Fourier transform infrared (FTIR) instruments have demonstrated the ability to detect these deposits, but FTIR instruments require contact with the surface, which is time consuming, sometimes impractical and potentially results in contamination. This Note describes a new non-contact technique, using quantum cascade laser spectroscopy that in real time can detect thin deposits of silicone.

Introduction
Infrared spectroscopy is a well established technique for detection and identification of contaminants on surfaces, in particular metallic surfaces. Detection levels can be as low as fractions of micrograms, depending on factors such as viewing/measurement angles and use of a polarized infrared beam. Detection of silicone films is an important application. For example, silicone release coatings are applied to surfaces to facilitate the manufacture of carbon-fiber/epoxy laminating materials. The silicone is supposed to remain on the fabricating equipment but in some cases it will migrate in small quantities to the fabricated material, which becomes problematic. For example, if the fabricated material is subsequently painted or otherwise coated, this silicone residue will result in poor adhesion affecting the quality, appearance and longevity of the coating. Figure 1: LaserScan Analyzer Also the silicon coatings

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Phone (508) 251-3100, Fax (508) 251-3171, www.blockeng.com

on the fabricating equipment must be monitored and maintained for the equipment to perform properly. This application note focuses on the use of Block Engineerings LaserScan Analyzer (Fig. 1) as a handheld spectrometer, based on quantum cascade laser (QCL) technology, for detecting and quantifying silicone film thicknesses.

Proposed Solution LaserScan Analyzer Technology

The LaserScan Analyzer, shown in Figure 1, is a revolutionary, handheld instrument from Block Engineering (Marlborough, MA) that can be used as an ideal tool for inspection of surfaces to detect the presence of silicone, validate its removal or chemically analyze the properties of any films on the surface. For example, it can be used by a production engineer to examine metal surfaces and provide rapid feedback for the presence of residual silicones on surfaces that are being prepared for bonding or painting. In another potential application, this instrument can be used in a noncontact fashion to evaluate new silicone materials by analyzing adhesion properties and chemical composition changes during production or application. The LaserScan Analyzer is the result of many years of development at Block Engineering and utilizes infrared spectroscopy. Infrared technology has been used for decades under laboratory conditions and some of the most common instruments using it are FTIR spectrometers. FTIR methods have been used to detect silicone, but these instruments use a diffuse infrared source so for these to work effectively they either have to make contact with the surface (use of ATR methods) or the measurement head has to get very close (within a centimeter or so) to the surface which creates a potential for further contamination, due to accidental contact. Because the LaserScan QCL technology uses a collimated, but eye safe, laser, it can measure residues on surfaces from distances of six inches to several feet depending on the application. The fundamental principle behind this technology is that, when infrared light reflects off of substances, it gets absorbed or reflected at rates that are absolutely unique to and characteristic of the substance. Therefore, when the reflected light is collected by the LaserScans built-in detectors, a fingerprint-like pattern emerges, which contains all the necessary information for detection or analysis of the substance. Built-in libraries are typically used to pattern and provide real-time detection or analysis. Furthermore, LaserScan is a lightweight handheld unit that provides readings in seconds.

Experimental Results
In this application note three samples of methyl silicone were dissolved in n-Hexane 97%. Sample A was 26 mg/mL; B was 50 mg/mL; C was 70 mg/mL. A micro-syringe was used to apply 0.01mL of each sample on a diffused gold substrate. The Hexane

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completely evaporated in 30 minutes leaving concentrations of 173 g/cm2 for sample A; 313 g/cm2 for sample B; 438 g/cm2 for sample C. The three samples were then examined with the LaserScan at a standoff distance of 6 inches.

Figure 2: Spectrum of silicone film on surface at 6 inches standoff distance (surface concentration of approximately 438 g/cm) Figure 2 shows the silicone spectrum for Sample C. As can be seen there are distinctive features including a strong feature at 1256 cm-1.

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Figure 3: Projections for Limit of Detection (LOD) estimated at 4.5 g/cm today (future projections to <1 g/cm)

Figure 3 shows a plot of absorption at wavelength 1256 cm-1 for each sample. Extrapolating the data points implies a limit of detection of 4.5 g/cm2, which is sufficient for most applications. Future versions of LaserScan currently under development should reduce the LOD to <1 g/cm2, if needed.

Conclusions
This application note demonstrates that Blocks LaserScan is the optimal tool for the standoff measurement of silicone films on surfaces. LOD of 4.5 g/cm2 on a metal surface has been demonstrated. LaserScan provides a new tool for production engineers and quality control departments tasked with ensuring the proper and effective use of silicone in important industrial applications. Future LaserScan devices will be much lighter (flashlight size) and more sensitive (projected LOD <1 g/cm).