Detection dispersion

Pan, G. and Taam, W. (2002). On generalized linear model method for detecting dispersion effects in unreplicated factorial designs. Journal of Statistical Computation and Simulation, 72, 431-450. 

The most commonly used technique to qualify filler dispersibility is to study light reflectivity of clean-cut mixes. Some apparatuses have been developed to evaluate filler dispersion using a calibrated set of reference mixes (Dispergrader). However, such characterization mainly detects dispersion defects of a few tens of microns, and direct comparison of carbon black and silica mixes has to be done cautiously. In any case, it is necessary to make a mix, which means choosing a formula, a mixer, and mixing conditions thus the result cannot be considered as an intrinsic dispersibility measurement of the filler, but just reflects the dispersibility of the filler in one mix with a set of mixing conditions. 

Interpreting radioactive tracer data is complicated by the flow structure, injection pulse and detector geometry. Detection dispersion arises from collimator geometry... 

Diode array detection (dispersive Fig. 3) offers the advantage of the absence of moving parts, extending the longevity and reliability of such systems compared to more traditional spectrophotometers. The main advantage of these instruments is the rapidity with which data can be collected (e.g., on the millisecond scale versus the traditional scanning instrument that makes spectral measurements on the seconds to minutes scale). 

Three of the four liquid rubbers produced, upon euring, a dispersion of second-phase rubber-rich particles in the polyester resin matrix, whereas the compatible rubber did not produce any detectable dispersion even at relatively high content. 

The detectable limits for a dispersion apparatus are a few g-g/g, and vary according to the environment around from a few pg/g for heavy elements in light matrices to a few mg/g for light elements. 

Let us consider the calculation of sensitivity threshold in the case when the cracks are revealing by PT method. Constant distance H between crack s walls along the whole defect s depth is assumed for the simplicity. The calculation procedure depends on the dispersity of dry developer s powder [1]. Simple formula has to be used in the case when developer s effective radius of pores IC, which depends mainly on average particle s size, is smaller than crack s width H. One can use formula (1) when Re is small enough being less than the value corresponding maximum sensitivity (0,25 - 1 pm). For example. Re = 0,25 pm in the case when fine-dispersed magnesia oxide powder is used as the developer. In this case minimum crack s width H that can be detected at prescribed depth lo is calculated as... 

While a laser beam can be used for traditional absorption spectroscopy by measuring / and 7q, the strength of laser spectroscopy lies in more specialized experiments which often do not lend themselves to such measurements. Other techniques are connnonly used to detect the absorption of light from the laser beam. A coimnon one is to observe fluorescence excited by the laser. The total fluorescence produced is nonnally proportional to the amount of light absorbed. It can be used as a measurement of concentration to detect species present in extremely small amounts. Or a measurement of the fluorescence intensity as the laser frequency is scaimed can give an absorption spectrum. This may allow much higher resolution than is easily obtained with a traditional absorption spectrometer. In other experiments the fluorescence may be dispersed and its spectrum detennined with a traditional spectrometer. In suitable cases this could be the emission from a single electronic-vibrational-rotational level of a molecule and the experimenter can study how the spectrum varies with level. 

One interesting new field in the area of optical spectroscopy is near-field scaiming optical microscopy, a teclmique that allows for the imaging of surfaces down to sub-micron resolution and for the detection and characterization of single molecules [, M]- Wlien applied to the study of surfaces, this approach is capable of identifying individual adsorbates, as in the case of oxazine molecules dispersed on a polymer film, illustrated in figure Bl.22,11 [82], Absorption and emission spectra of individual molecules can be obtamed with this teclmique as well, and time-dependent measurements can be used to follow the dynamics of surface processes. 

Figure Bl.22.11. Near-field scanning optical microscopy fluorescence image of oxazine molecules dispersed on a PMMA film surface. Each protuberance in this three-dimensional plot corresponds to the detection of a single molecule, the different intensities of those features being due to different orientations of the molecules. Sub-diffraction resolution, in this case on the order of a fraction of a micron, can be achieved by the near-field scaiming arrangement. Spectroscopic characterization of each molecule is also possible. (Reprinted with pennission from [82]. Copyright 1996 American Chemical Society.)...

The array system is discussed in Chapter 29. With array detection, resolution of m/z values depends both on the analyzer and the collector. Historically, the method for recording ions dispersed in space was to use a photographic plate, which was placed in the focal plane such that all ions struck the photographic plate simultaneously but at different positions along the plate, depending on m/z value. This method of detection is now rarely used because of the inconvenience of having to develop a photographic plate. 

There is potential confusion in the use of the word array in mass spectrometry. Historically, array has been used to describe an assemblage of small single-point ion detectors (elements), each of which acts as a separate ion current generator. Thus, arrival of ions in one of the array elements generates an ion current specifically from that element. An ion of any given m/z value is collected by one of the elements of the array. An ion of different m/z value is collected by another element. Ions of different m/z value are dispersed in space over the face of the array, and the ions are detected by m/z value at different elements (Figure 30.4). 

Consider again two detection elements, and suppose an ion beam has been dispersed in time such that ions of m/z 100 arrive at each of several elements (Figure 30.5). In this TOF mode, the next ion of m/z 101 has not yet arrived, and the ion of m/z 99 has arrived previously. Although the m/z ions are dispersed in time over a region of space and strike different elements of the detector, they are collected and monitored simultaneously because all of the microchannels are electronically connected. The operation of the microchannel plate is much easier than that of the array because all the elements are monitored as one at the plate, while each element must be monitored separately in the array. The microchannel plate detector is tremendously useful for those cases in which ions... 

A multipoint ion collector (also called the detector) consists of a large number of miniature electron multiplier elements assembled, or constructed, side by side over a plane. A multipoint collector can be an array, which detects a dispersed beam of ions simultaneously over a range of m/z values and is frequently used with a sector-type mass spectrometer. Alternatively, a microchannel plate collector detects all ions of one m/z value. When combined with a TOP analyzer, the microchannel plate affords an almost instantaneous mass spectrum. Because of their construction and operation, microchannel plate detectors are cheaper to fit and maintain. Multipoint detectors are particularly useful for situations in which ionization occurs within a very short space of time, as with some ionization sources, or in which only trace quantities of any substance are available. For such fleeting availability of ions, only multipoint collectors can measure a whole spectrum or part of a spectrum satisfactorily in the short time available. 

The ions in a beam that has been dispersed in space according to their various m/z values can be collected simultaneously by a planar assembly of small electron multipliers. All ions within a specified mass range are detected at the same time, giving the array detector an advantage for analysis of very small quantities of any one substance or where ions are produced intermittently during short time intervals. 

In a mass spectrometer, ions can arrive at a multipoint collector as a spatially dispersed beam. This means that all ions of different m/z values arrive simultaneously but separated in space according to each m/z value. Each element of the array, depending on its position in space, detects one particular m/z value (see Chapter 29, Array Collectors ). 

Alternatively, the ions in a mass spectrometer can also arrive at a multipoint collector as a temporally dispersed beam. Therefore, at any point in time, all ions of the same m/z value arrive simultaneously, and different m/z values arrive at other times. Ail elements of this collector detect the arrival of ions of one m/z value at any one instant of time. This type of detector, which is also an array, is called a microchannel plate collector of ions. 

In a beam of ions separated in time according to m/z value, the total time taken for ions of different m/z values to arrive at a microchannel plate is so short (about 30 psec) that the spectrum appears to have been obtained instantaneously. Thus, for practical purposes, the array and microchannel plate collectors produce an instantaneous mass spectrum, even though the first detects a spatially dispersed set of m/z values and the second detects a temporally dispersed set. 

As in all Fourier transform methods in spectroscopy, the FTIR spectrometer benefits greatly from the multiplex, or Fellgett, advantage of detecting a broad band of radiation (a wide wavenumber range) all the time. By comparison, a spectrometer that disperses the radiation with a prism or diffraction grating detects, at any instant, only that narrow band of radiation that the orientation of the prism or grating allows to fall on the detector, as in the type of infrared spectrometer described in Section 3.6. 

In outline, the method used is to pass the monochromatic radiation through the gaseous sample and disperse and detect the scattered radiation. Usually, this radiation is collected in directions normal to the incident radiation in order to avoid this incident radiation passing to the detector. 

Figure 8.28 shows how the X-rays fall on the solid or liquid sample which then emits X-ray fluorescence in the region 0.2-20 A. The fluorescence is dispersed by a flat crystal, often of lithium fluoride, which acts as a diffraction grating (rather like the quartz crystal in the X-ray monochromator in Figure 8.3). The fluorescence may be detected by a scintillation counter, a semiconductor detector or a gas flow proportional detector in which the X-rays ionize a gas such as argon and the resulting ions are counted.

An energy dispersive spectrometer is cheaper and faster for multielement analytical purposes but has poorer detection limits and resolution. 

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