Direct insertion probe pyrolysis mass

Direct insertion probe pyrolysis mass spectrometry (DPMS) utilises a device for introducing a single sample of a solid or liquid, usually contained in a quartz or other non-reactive sample holder, into a mass spectrometer ion source. A direct insertion probe consists of a shaft having a sample holder at one end [70] the probe is inserted through a vacuum lock to place the sample holder near to the ion source of the mass spectrometer. The sample is vaporized by heat from the ion source or by heat from a separate heater that surrounds the sample holder. Sample molecules are evaporated into the ion source where they are then ionized as gas-phase molecules. In a recent study, Uyar et al. [74] used such a device for studying the thermal stability of coalesced polymers of polycarbonate, PMMA and polylvinyl acetate) (PVAc) [75] and their binary and ternary blends [74] obtained from their preparation as inclusion compounds in cyclodextrins. 

Figure 4 Typical instrumental configurations for pyrolysis electron-impact ionization mass spectrometry direct insertion probe pyrolysis mode (upper) and Curie-point pyrolysis mode (lower). Reproduced by permission of Elsevier Science from Meuzelaar HLC, Windig W, Huff SM and Richards JM (1986). Analytica Chimica Acta 190 119-132.

In direct insertion techniques, reproducibility is the main obstacle in developing a reliable analytical technique. One of the many variables to take into account is sample shape. A compact sample with minimal surface area is ideal [64]. Direct mass-spectrometric characterisation in the direct insertion probe is not very quantitative, and, even under optimised conditions, mass discrimination in the analysis of polydisperse polymers and specific oligomer discrimination may occur. For nonvolatile additives that do not evaporate up to 350 °C, direct quantitative analysis by thermal desorption is not possible (e.g. Hostanox 03, MW 794). Good quantitation is also prevented by contamination of the ion source by pyrolysis products of the polymeric matrix. For polymer-based calibration standards, the homogeneity of the samples is of great importance. Hyphenated techniques such as LC-ESI-ToFMS and LC-MALDI-ToFMS have been developed for polymer analyses in which the reliable quantitative features of LC are combined with the identification power and structure analysis of MS. 

Pyrolysis mass spectroscopy was conducted with a Hewlett-Packard model 5985B gas chromatograph/quadrupole mass spectrometer, operated at sslO- Torr and 70eV electron-impact ionization energy. Samples were introduced into the mass spectrometer via a glass lined direct insertion probe (DIP). The samples were decomposed in the DIP to a nominal temperature of 300°C at a heating rate of 30°C/min. 

In pyrolysis-mass spectrometry (Py-MS) the pyrolysate is directly transferred to a mass spectrometer and analyzed, generating a complex spectrum. The sample introduction can be done using various techniques. One simple technique is the direct insertion probe (DIP) where the sample is deposited on an insert that has the capability of heating the sample and of introducing the pyrolysate directly into the ion source of the mass spectrometer (see e.g. [1]). Another technique is the Curie point Py-MS where an attachment to the mass spectrometer allows the sample to be placed in a radio frequency (RF) region continued by an expansion chamber connected to the ion source. The sample is pyrolyzed and the pyrolysate ionized and analyzed in the MS instrument. A schematic diagram of a Curie point Py-MS system is shown in Figure 3.3.2. 

Direct insertion probe mass spectrometry (DIP-MAS) analyses of poly(methyl methacrylate) (PMMA), poly(vinyl acetate) (PVAc), and their coalesced and precipitated blends were performed [51] (see Fig. 21). The fact that the pyrolysis mass... 

The use of a direct insertion probe for pyrolysis-MS requires that the mass spectrometer be equipped with an inlet for a solids probe. Most mass spectrometers used in analytical labs are configured as detectors for gas chromatographs and are relatively simple and inexpensive, but are rarely equipped with a probe inlet. The only way for a sample compound to enter a mass spectrometric detector is via the capillary column inlet, configured to accept a piece of fused silica. Nevertheless, if the capillary column is removed and replaced with a piece of fused silica sufficiently restrictive to limit the flow into the mass spectrometer, pyrolysis-MS data may be... 

In principle, any type of magnetic or quadrupole mass spectrometer can be utilized for the analytical pyrolysis of organic materials, if a direct introduction system capable of producing a desired tempera-ture/time profile is available. For example, direct insertion probes (DIPs) and direct exposure probes (DEPs) are Avidely used for sample introduction and such probes are supplied with control units that allow heating and temperature programming of the sample up to 500-800°C. Therefore, such modules should be considered as the most readily available probes for Py-MS studies. 

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