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B. Qualitative Analysis of Microsamples

1. Single textile fibers

 FTIR-PAS offers some unique advantages
for microsample
analysis over FTIR microscopy:

1. No pressing of samples is required to reduce optical
density. This avoids the destruction of evidence in forensic
analyses, and questions of reproducibility and sample alteration
posed by the pressing operation. The nondestructive character
of FTIR-PAS allows analyses confirmation by other techniques
such as optical or electron microscopy.
2. The delicate optical alignment and aperturing
of FTIR microscopy is avoided because FTIR-PAS microsampling
can be done with a beam focal spot size that is much larger than
the sample since only the portion of the beam that impinges on
the sample generates a photoacoustic signal.
3. The spectral range of measurements is not limited
by the cut-off of narrow band MCT detectors commonly used in
FTIR microscopy. The extended spectral range of FTIR-PAS microsample
spectra allows better spectral differentiation between difficult
samples such as nylons.
4. FTIR-PAS spectra of fibers have more easily discernible
detail because normally weak but definitive bands are more prominent
due to truncation of strong bands by photoacoustic signal saturation
and to enhanced structure at low wavenumbers from more efficient
signal generation at low frequencies.

A key consideration in FTIR-PAS microsample analyses
is mounting the sample so that it is surrounded by helium gas
for efficient signal generation. Fig. 14 shows devices supplied
by MTEC that are used to mount single fibers and particles for
FTIR-PAS analyses. Tweezers are used to mount fibers in spring
loaded split rings before placement in the sample cup. In front
of the sample holder is a fixture which holds the ring with either
a white or black centering pin to provide a contrasting background
during mounting of fibers. In the procedure, fibers are either
attached by pressure sensitive adhesive to the arms of the device
shown in Fig. 14 in front of the ring fixture, or fibers can
be manipulated with tweezers during mounting. This operation
can be done using an illuminated bench magnifier with a contrasting
background. A microscope is not required. In Fig. 15 a black
thread depicts a fiber being mounted and placed in the sample
holder over a covered desiccant cup. The desiccant cup is shown
in Fig. 14 on the left side of the ring fixture. A magnesium
perchlorate desiccant and a dry helium gas atmosphere are required
in micro- sampling because otherwise the water vapor signal,
which is out-of-phase with the sample signal, can dominate the
sample signal and seriously degrade the spectrum. |