Laser-focusing techniques

One of two basic principles is employed in most commercial optical non-contact methods. The first is the laser-focusing technique, which works according to the same basic principle as a CD-player, and can best be described as an optical equivalent of the stylus... 

With the use of appropriate transmission optics, high focusing of the laser light is carried out and the extension of the optical probe is considerably reduced. Accordingly, laser-based techniques offer the possibility of measurements of high spatial resolution. 

Alternative approaches consist in heat extraction by means of thermal analysis, thermal volatilisation and (laser) desorption techniques, or pyrolysis. In most cases mass spectrometric detection modes are used. Early MS work has focused on thermal desorption of the additives from the bulk polymer, followed by electron impact ionisation (El) [98,100], Cl [100,107] and field ionisation (FI) [100]. These methods are limited in that the polymer additives must be both stable and volatile at the higher temperatures, which is not always the case since many additives are thermally labile. More recently, soft ionisation methods have been applied to the analysis of additives from bulk polymeric material. These ionisation methods include FAB [100] and LD [97,108], which may provide qualitative information with minimal sample pretreatment. A comparison with FAB [97] has shown that LD Fourier transform ion cyclotron resonance (LD-FTTCR) is superior for polymer additive identification by giving less molecular ion fragmentation. While PyGC-MS is a much-used tool for the analysis of rubber compounds (both for the characterisation of the polymer and additives), as shown in Section 2.2, its usefulness for the in situ in-polymer additive analysis is equally acknowledged. 

Initially, the reactor was to be built using silicon wafers, 92 but more recent efforts have focused on a stainless steel reactor. The reformer, 7.5 x 4.5 x 11.0 cm (371 cm ), houses up to 15 stainless steel plates (0.5 mm thick) with chemically etched microchannels and heating cartridges. Conventional and laser micromachining techniques were used to fabricate the reformer body. The microchannel dimensions are 0.05 x 0.035 x 5.0 cm . The reactor inlet was carefully designed to allow uniform flow conditions. ... 

However, the high frequency of the laser irradiation in the visible region may lead to photochemical reactions in the laser focus. Besides, fluorescence can often cover the whole Raman spectrum. Such problems can be avoided by using an excitation wavelength in the near-infrared (NIR) region, e.g. with an Nd YAG laser operating at 1064 nm. Deficits arising from the v dependence of the Raman intensity and the lower sensitivity of NIR detectors are compensated by the Fourier-Transform (IT) technique, which is widespread in IR spectroscopy . ... 

LA-ICP mass spectrometry is becoming the method of the choice for trace and isotope analysis of solid samples and is already the most important laser induced technique in inorganic mass spectrometry due to the advantage of direct solid sampling by focused laser irradiation on the sample surface and its ability to provide microscale information. 

The theory and instrumentation of Fourier transform mass spectrometry (FTMS) have been discussed extensively in this book and elsewhere [21-23]. All experiments were performed on a Nicolet prototype FTMS-1000 Fourier transform mass spectrometer previously described in detail [24] and equipped with a 5.2 cm cubic trapping cell situated between the poles of a Varian 15 in. electromagnet maintained at 0.85 T. The cell was constructed in our laboratory and utilizes two 80 transmittance stainless steel screens as the transmitter plates. This permits irradiation with a 2.5 kW Hg-Xe arc lamp, used in conjunction with a Schoeffel 0.25 m monochromator set for 10 nm resolution. Metal ions are generated by focusing the beam of a Quanta Ray Nd YAG laser (either the fundamental line at 1064 nm or the frequency doubled line at 532 nm) into the center-drilled hole (1 mm) of a high-purity rod of the appropriate metal supported on the transmitter screen nearest to the laser. The laser ionization technique for generating metal ions has been outlined elsewhere [25]-... 

In compiling the information in this chapter, I have relied heavily on several very comprehensive reviews that have appeared over the past few years [1-7]. In particular, the 1978 review by T irro et al. [1] is extremely thorough in describing the intra- and intermolecular photophysics and chemistry of upper singlet and triplet states. In fact, rather than reproduce the same details here, I direct the reader to this review for a summary of upper state behavior reported prior to 1978. (A description of azulene and thione anomalous fluorescence is included since these systems are the best-known systems that display upper state behavior.) I also direct readers to the reviews by Johnston and Scaiano [2] and Wilson and Schnapp [3] which focus on the chemistry of both upper triplet states and excited reaction intermediates as studied by laser flash photolysis (one- and two-color methods) and laser jet techniques. Also, Johnston s thorough treatment of excited radicals and biradicals [4] and the review of thioketone photophysics and chemistry by Maciejewski and Steer [5] are excellent sources of detailed information. 

The spatial resolving power is especially large, if the confocal technique is applied (Schrader et al., 1993, 1994). A focus of a laser beam is produced by a microscope objective of large numerical aperture at the spot of the sample to be investigated (Fig. 3.5-12). The radiation emerging from this spot is projected by the objective onto a diaphragm with a hole of the size of the projected laser focus. Only the radiation passing... 

Laser Ablation [7]. The modern method for quantitative solid analyses is carried out using a laser ablation technique (Figure 2.16). The laser, usually in the form of Nd YAG (Neodymium - Doped Yttrium Aluminium Garnet), is focused on to the surface of a sample which, by continuous pulsing, leads to vaporisation at that point and the vapour is transported directly to the plasma with argon for detection and quantification. Detection limits are... 

In a bimolecular solution reaction, the reactants A and B diffuse to a point close to one another at which reaction is possible. This process is called formation of the precursor complex. At this point, rearrangement of bond lengths and bond angles in the two reactants, and of the surrounding solvent molecules, can occur to form an activated complex or transition state between the reactants and products. As one would expect, the nature of this process depends on the specific reaction involved. It is the focus of the development of the theory of the elementary step in the reaction and the associated energy requirements. In some cases it has been studied experimentally using very fast laser spectroscopic techniques which provide time-resolved information about the elementary step in the femtosecond range. 

Eberly, J. H., P. Maine, D. Strickland, and G. Mourou, 1987, Laser Focus 23 (10), 84-90. Eisenthal, K. B., 1977, in Ultrashort Light Pulses—Picosecond Techniques and Applications,... 

In this chapter, we will focus on photosensitive systems that are used in free radical photopolymerization reactions. We will give the most exhaustive presentation of the commercially used or potentially interesting systems developed on a laboratory scale together with the characteristics of their excited-state properties. We will also show how modem time resolved laser spectroscopy techniques and quantum mechanical calculations allow to probe the photophysical/photochemical properties as well as the chemical reactivity of a given photoinitiating system. 

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