Effect of Particle Size and Modulation Frequency on the Photoacoustic Spectra of Silica Powders

"Investigations of the infrared spectra of crystalline and amorphous silica particles of different sizes (0.05, 5, 10, 15, 30, 45, and 260 um) in the range of 400-4000 cm-1 using Fourier transform infrared/photoacoustic spectroscopy we reported. The change in the intensity I of the signal with porosity e of powders follows the e/(1 - e) dependence for strong bands and e dependence for weaker bands as pre¬dicted by the theory of McGovern of al. For strong bands, I also follows the empirical relation I ~ D-n, where D Is the particle diameter in cm and n = 0.34-0.42. The anomalous positive frequency dependence of I on the modulation fre¬quency f observed for the stronger bands in the 45-pm and 260-pm particles Is believed to result from saturation. Some observations on the effect of changing the background from (carbon black) powder to pellet are also made.INTRODUCTIONSince the publication of the Rosencwaig—Gersho (RG) theory on the photoacoustic effect in solids (1, 2), Fourier transform infrared/photoacoustic spectroscopy (FTIR/PAS) has become an important technique for obtaining the IR spectra of surfaces and materials in their natural state (1-12). In the one-dimensional RG theory, the incident radiation, modulated at frequency f, is absorbed by the material to a depth pp = 1/B (B = absorption coefficient), thus setting up temperature variations in the material. These variations heat the adjacent gas/solid interface leading to the pressure fluctuations of the gas above the sample, which in turn is detected by microphone as a PA signal. The thermal wave originating from no deeper than the thermal diffusion length(2k/npcf) 1/2 in the material contributes to the PA signal (here k, p, and c are respectively the thermal conductivity, density, and specific heat of the material). Since u2, can be varied by varying the experimental parameter f, depth pro¬filing by PAS is possible and a number of papers on this subject have appeared in recent years (2-10). Another im¬portant phenomenon is saturation which occurs when the material thickness 1> u> us (1-12).The original promise of PAS for use with powder samples, without the need to ""prepare"" samples as in FTIR spectros-copy, has not yet been fully realized because of several com¬plications. Theoretical works by Monchalin et al. (13) and McGovern et al (14) showed that the interstial gas in the voids of the powders can act as amplifier and that, for the same mass, a finer powder is expected to yield higher PA signal than a coarser powder. Although in a number of earlier studies (15-21) an increase of PA signal with decreasing particle size has been observed, a quantitative check on the equations developed by McGovern et al. (14) has not yet been made. It is necessary to understand the particle size effects in PAS if the promise of PAS for IR spectroscopy of powders is to be realized. In this paper, we report results of a detailed study on the PAS of silica powders for the particle size range of 0.05-260 um and compare the results with theory (14). We have also investigated the frequency dependence of the variousIR modes in these powders and show that the saturation phenomenon affects at least some of the observations. Some observations on the effects of pellet vs powder background are also reported (22-24). Details of these findings are presented and discussed in this paper."