Probe tip

There are many other experiments in which surface atoms have been purposely moved, removed or chemically modified with a scanning probe tip. For example, atoms on a surface have been induced to move via interaction with the large electric field associated with an STM tip [78]. A scaiming force microscope has been used to create three-dimensional nanostructures by pushing adsorbed particles with the tip [79]. In addition, the electrons that are tunnelling from an STM tip to the sample can be used as sources of electrons for stimulated desorption [80]. The tuimelling electrons have also been used to promote dissociation of adsorbed O2 molecules on metal or semiconductor surfaces [81, 82]. 

A dynamic-FAB probe tip incorporating a screen and wick assembly at the target surface. 

More recent versions of this type of probe include some refinements, such as the provision of a wick to aid evaporation of the solvent and matrix from the probe tip (Figure 13.5). Such improvements have allowed greater flow rates to be used, and rates of 1 to 10 ml/min are possible. For these sorts of low flow rates, minibore LC columns must be employed. 

By passing a continuous flow of solvent (admixed with a matrix material) from an LC column to a target area on the end of a probe tip and then bombarding the target with fast atoms or ions, secondary positive or negative ions are ejected from the surface of the liquid. These ions are then extracted into the analyzer of a mass spectrometer for measurement of a mass spectrum. As mixture components emerge from the LC column, their mass spectra are obtained. 

Another development arising from FAB has been its transformation from a static to a dynamic technique, with a continuous flow of a solution traveling from a reservoir through a capillary to the probe tip. Samples are injected either directly or through a liquid chromatography (LC) column. The technique is known as dynamic or continuous flow FAB/LSIMS and provides a convenient direct LC/MS coupling for the on-line analysis of mixtures (Figure 40.2). 

This equation is appHcable for gases at velocities under 50 m/s. Above this velocity, gas compressibiUty must be considered. The pitot flow coefficient, C, for some designs in gas service, is close to 1.0 for Hquids the flow coefficient is dependent on the velocity profile and Reynolds number at the probe tip. The coefficient drops appreciably below 1.0 at Reynolds numbers (based on the tube diameter) below 500. 

Before taking the sample train to the test site, it is wise to prepare the operating curves for the particular job. With most factory-assembled trains, these curves are a part of the package. If a sampling train is assembled from components, the curves must be developed. The type of curves will vary from source to source and from train to train. Examples of useful operating curves include (1) velocity versus velocity pressure at various temperatures (6), (2) probe tip velocity versus flowmeter readings at various temperatures, and (3) flowmeter calibration curves of flow versus pressure drop. It is much easier to take an operaHng point from a previously prepared curve than to take out a calculator and pad to make the calculahons at the... 

For sampling particulate matter, one is dealing with pollutants that have very different inertial and other characteristics from the carrying gas stream. It becomes important, therefore, to sample so that the same velocity is maintained in the probe tip as exists in the adjacent gas stream. Such sampling is called isokinetic. Isokinetic sampling, as well as anisokinetic sampling, is illustrated in Fig. 13-3. 

If the probe velocity is less than the stack velocity, particles will be picked up by the probe, which should have been carried past it by the gas streamlines. The inertia of the particles allows them to continue on their path and be intercepted. If the probe velocity exceeds the stack velocity, the inertia of the particles carries them around the probe tip even though the carrying gases are collected. Adjustment of particulate samples taken anisokinetically to the correct stack values is possible if all of the variables of the stack gas and particulate can be accounted for in the appropriate mathematical equations. 

Electrons can penetrate the potential barrier between a sample and a probe tip, producing an electron tunneling current that varies exponentially with the distance. 

The STM uses this eflFect to obtain a measurement of the surface by raster scanning over the sample in a manner similar to AFM while measuring the tunneling current. The probe tip is typically a few tenths of a nanometer from the sample. Individual atoms and atomic-scale surface structure can be measured in a field size that is usually less than 1 pm x 1 pm, but field sizes of 10 pm x 10 pm can also be imaged. STM can provide better resolution than AFM. Conductive samples are required, but insulators can be analyzed if coated with a conductive layer. No other sample preparation is required. 

Two forms of interface have been commercially developed [7] which allow analytes in a flowing liquid stream - it has to be pointed out, not necessarily from an HPLC system (see below) - to be ionized by using FAB. These are essentially identical except for that part where the HPLC eluate is bombarded with the heavy-atom/ion beam. Both of these interfaces consist of a probe in the centre of which is a capillary which takes the flowing HPLC eluate. In the continuous-flow FAB interface (Figure 4.3), the column eluate emerges from the end of the capillary and spreads over the probe tip, while in the frit-FAB interface the capillary terminates in a porous frit onto which the atom/ion beam is directed. 

Excess mobile phase has to be removed from the probe tip to allow its replenishment and this may be accomplished in a number of ways, for example, with an absorbent pad situated adjacent to the area subjected to atom/ion bombardment. 

The use of low flow rates introduces two further practical problems. The first is the inability to maintain stable conditions at the end of the probe, hence resulting in fluctuations in ion current, as experienced when droplets are formed on the moving belt. As the liquid emerges onto the probe tip, it experiences the high vacuum and begins to evaporate, with a consequent reduction in the temperature of the probe tip. Sufficient heat must therefore be applied to prevent freezing of the mobile phase and this helps stabilize ion production. 

It is possible to study thermally labile materials using this type of interface since the only heat applied to the probe tip is that required to prevent freezing of the mobile phase as it evaporates. 

The presence of the matrix can cause chromatographic problems if added to the mobile phase before the column, especially if this is of small diameter. The low flow rates that are used require an increased concentration of matrix to be present in the mobile phase to ensure an appropriate amount reaches the probe tip. 

Recent demands for polymeric materials request them to be multifunctional and high performance. Therefore, the research and development of composite materials have become more important because single-polymeric materials can never satisfy such requests. Especially, nanocomposite materials where nanoscale fillers are incorporated with polymeric materials draw much more attention, which accelerates the development of evaluation techniques that have nanometer-scale resolution." To date, transmission electron microscopy (TEM) has been widely used for this purpose, while the technique never catches mechanical information of such materials in general. The realization of much-higher-performance materials requires the evaluation technique that enables us to investigate morphological and mechanical properties at the same time. AFM must be an appropriate candidate because it has almost comparable resolution with TEM. Furthermore, mechanical properties can be readily obtained by AFM due to the fact that the sharp probe tip attached to soft cantilever directly touches the surface of materials in question. Therefore, many of polymer researchers have started to use this novel technique." In this section, we introduce the results using the method described in Section 21.3.3 on CB-reinforced NR. 

NR with standard recipe with 10 phr CB (NR 10) was prepared as the sample. The compound recipe is shown in Table 21.2. The sectioned surface by cryo-microtome was observed by AFM. The cantilever used in this smdy was made of Si3N4. The adhesion between probe tip and sample makes the situation complicated and it becomes impossible to apply mathematical analysis with the assumption of Hertzian contact in order to estimate Young s modulus from force-distance curve. Thus, aU the experiments were performed in distilled water. The selection of cantilever is another important factor to discuss the quantitative value of Young s modulus. The spring constant of 0.12 N m (nominal) was used, which was appropriate to deform at rubbery regions. The FV technique was employed as explained in Section 21.3.3. The maximum load was defined as the load corresponding to the set-point deflection. 

The final component of the AFM is the tip-sample approach mechanism. Bringing the probe tip and the sample within interaction range in a nondestructive manner involves mounting one surface on an approach mechanism with subangstrom sensitivity. Most approach devices normally combine some form of stepper or slider with single step sizes of the order of microns, with a piezo device providing displacements of the order of one tenth of an angstrom up to a maximum of several microns. In microscopy mode, the piezo device... 

Demming, F., Jersch, J., Dickmatm, K.and Geshev. P. I. (1998) Calculation of the field enhancement on laser-illuminated scanning probe tips by the boundary element method. Appl. Rhys. B, 66, 593-598. 

In this section, we will describe some experiments which we have performed using the above-mentioned nano-Raman microscope. Figure 2.6a shows the Raman spectmm of an adenine nanocrystal of height 7 nm and width 30 nm [19]. Several Raman bands are observed as the probe tip is near enough to the sample (AFM operation is made in contact mode). These bands, except the one appearing at 924 cm, are assigned as the vibrational modes, inherent to the adenine molecule, according to the molecular orbital calculation. For examples, two major bands, one at... 

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