Design and performance of an evolved gas analysis ion attachment mass spectrometer

We designed a simple evolved gas analysis (EGA) system to act as a sampler between solid samples at atmospheric pressure and the high vacuum inside a mass spectrometer. The newly designed stainless steel system is simple, small and rugged and fulfills all the basic requirements for EGA. The temperature is programmable with 60°C/min as the maximum heating rate and the temperature range is up to 600°C. With this system coupled with lithium ion attachment mass spectrometry (IAMS), it is possible to study the temperature‐programmed decomposition of a number of solid materials by detecting any chemical species on a real‐time basis. For illustrative purposes, EGA‐IAMS experiments of polyethylene polymers have been conducted. Copyright © 2010 John Wiley & Sons, Ltd.     

Development of new pyrolysis–GC/MS system incorporated with on-line micro-ultraviolet irradiation for rapid evaluation of photo, thermal, and oxidative degradation of polymers

A new pyrolysis–GC/MS system incorporating with on-line micro-ultraviolet (UV) irradiation was developed to make rapid evaluation of the synergistic material deterioration during UV irradiation under thermal and oxidative atmospheres. The basic effectiveness of the system was demonstrated by polystyrene, polypropylene and polycarbonate as the test samples. The volatile products evolved during deterioration of the polymers were analyzed on-line by thermal desorption GC/MS, and then the residual degraded polymers were analyzed by evolved gas analysis (EGA) and/or Py–GC/MS to obtain specific thermograms and pyrograms. Based on these results, the deterioration mechanism of the polymeric materials during irradiation under thermal and oxidative atmosphere can be evaluated using a sub-milligram polymer sample within a relatively short period of time.     

Thermoanalytical characterization of polymers: A comparative study between thermogravimetry and evolved gas analysis using a temperature-programmable pyrolyzer

Evolved gas analysis (EGA) was carried out on 15 synthetic polymer samples using a temperature programmable pyrolyzer as a heating unit which was on-line coupled with a MS detector. A deactivated stainless steel tube and a vent free adapter were used to couple the pyrolyzer with the MS detector, and they were placed in a GC oven at 300°C to avoid condensation of evolved gases with high boiling point. Thermograms of polystyrene measured by this system (Py-EGA-MS) showed shifts of the peak temperature to the higher temperature region as the sample mass increased. It was found that the S/N ratios of EGA thermograms were 420-fold superior to those of differential thermogravimetry (DTG) thermograms for the same sample mass of 0.20 mg. Since a good linear relationship was obtained between peak temperatures obtained by Py-EGA-MS and DTG, it can be concluded that Py-EGA-MS can be used to obtain reliable data on thermal properties of samples with high sensitivity and using less sample.     

Sol-Gel Synthesis and Pyrolysis Study of Oxyfluoride Silica Gels

Silicon oxyfluoride materials are synthesized by the sol-gel method using triethoxyfluorosilane as precursor, bearing the Si—F bond. SiO_(2–0.5x) F _x gel preparation requires peculiar experimental control of hydrolysis and condensation reactions. Maintenance of the Si—F bond during gelling, heating and aging was studied in the case of processes carried out under an argon atmosphere or in air. Fluorine contents in resulting samples were quantified by FT-IR and X-ray photoelectron spectroscopy (XPS); specific surface area and porosity of powdered samples were determined by N₂ adsorption. The thermal stability of oxyfluoride gels was studied by thermogravimetric-mass spectrometric (TG-MS) coupled analyses during heat treatment, under He flow. Mass spectra recorded during principal weight losses indicate the release of variously fluorinated silicon species resulting from Si—F/Si—O exchange reactions. The evolution of these species was observed at different temperatures, depending on gelling conditions. In particular, degradation of Si—F moieties was prominent for gels aged in air, whereas samples processed under an argon atmosphere preserve the Si—F bond up to 300°C.     

Thermal behavior of Fe<Subscript>2</Subscript>O<Subscript>3</Subscript>/TiO<Subscript>2</Subscript> mesoporous gels

Summary Titania-based photocatalytic materials were prepared by sol-gel method using Fe³⁺ and polyethyleneglycol (PEG₆₀₀) as additives. Thermogravimetry (TG), differential thermal analysis (DTA) and evolved gas analysis (EGA) with MS detection were used to elucidate processes that take place during heating of Fe³⁺ containing titania gels. The microstructure development of the Fe₂O₃/TiO₂ gel samples with and without PEG₆₀₀ admixtures was characterized by emanation thermal analysis (ETA) under in situ heating in air. A mathematical model was used for the evaluation of ETA results. Surface area and porosity measurements of the samples dried at 120&deg;C and the samples preheated for 1 h to 300 and 500&deg;C were compared. From the XRD measurements it was confirmed that the crystallization of anatase took place after thermal heating up to 600&deg;C.     

Ageing and thermal stability studies on quasi-solid composite electrolytes for Grätzel-type solar cells

Loss of volatile components from two types of quasi-solid gel electrolytes to be used in Grätzel (or dye-sensitized, DSSC)-type alternative solar cells are checked time to time by thermogravimetry (TG) to follow the stability or changes of composites during storage at ambient. One of the gel samples, labeled as P2000 and based on UreaSil 2000, a 3D-cage precursor compound, has been found quite stable, while the related P230 sample based on UreaSil 230 seems to have a bit higher deviation in heterogeneity and some tendencies losing gradually from its volatile content, time to time. In addition, two online coupled evolved gas analytical tools (TG–EGA–FTIR and TG/DTA–EGA–MS) are applied to check the gel electrolytes for thermal vaporization, degradation, and decomposition processes as a function of temperature during dynamic heating in air. Initial minor elimination of ethyl acetate has been detected by both in situ coupled mass spectroscopy and FTIR spectroscopic gas cell. According to both evolved gas analytical systems, the other liquid ingredients, acetic acid (AcOH) and sulfolane are also released in the order of their volatility. Above 300 °C, an oxidative thermal degradation of UreaSil-type host matrices is indicated by the occurrence of, among others, formaldehyde or ammonia for electrolyte samples P2000 and P230, respectively. Evolution of various alkyl iodides with short chain length has only been detected by the mass spectroscopic evolved gas analysis method only.     

Thermal and kinetic study of dehydration and decomposition processes for copper intercalated γ-zirconium and γ-titanium phosphates

Thermal dehydration and decomposition processes of some intercalation compounds were studied by simultaneous TG/DSC and evolved gas analysis (EGA). γ-Zirconium and γ-titanium phosphates were intercalated with 1,10-phenanthroline and subsequently reacted with copper ions to form the complex in situ. Reaction mechanisms for thermal decomposition of all the materials were investigated and proposed according to the mass losses recorded by TG and confirmed by EGA (TG-FTIR). The Ozawa-Flynn-Wall isoconversional method provided dependencies of activation energy on the degree of conversion. A “single point” model-free method was also applied using Kissinger equation and the derived results were compared to those of the former method.     

DTA—TG—MS in the investigation of clays: Quantitative determination of H2O, CO and CO2 by evolved gas analysis with a mass spectrometer

A thermoanalyzer (Mettler) combined with a quadrupole mass spectrometer (Balzers) by a capillary inlet system allows simultaneous DTA, TG and evolved gas analysis in different atmospheres. Decomposition of CaC₂O₄·H₂O in air and argon, respectively, demonstrates the usefulness of the mass spectrometer for the quantitative determination of H₂O, CO₂ and CO. Decomposition of NaHCO₃ at a heating rate of 10°C min⁻¹ reveals that H₂O and CO₂ evolved simultaneously at a relatively low temperature (159°C) can also be determined quantitatively and nearly without retardation compared with the weight loss step. In the investigation of clays an example will be given of the usefulness of the described DTA—TG—MS in the quantitative interpretation of overlapping reactions.     

Applications of evolved gas analysis Part 2: EGA by mass spectrometry

The analytical applications of the evolved gas analysis (EGA) performed by mass spectrometry, for the period extending from 2001 to 2004, are collected in this review. By this technique, the nature of volatile products released by a substance subjected to a controlled temperature program is on-line determined, with the possibility to prove a supposed reaction, either under isothermal or under heating conditions.     

Applications of evolved gas analysis Part 1: EGA by infrared spectroscopy

The analytical applications of the evolved gas analysis (EGA) performed by infrared spectroscopy, for the period extending from 2001 to 2004, are collected in this review. By this technique, the nature of volatile products released by a substance subjected to a controlled temperature program are on-line determined, with the possibility to prove a supposed reaction, either under isothermal or under heating conditions.     

RNAA of trace iridium in Precambrian-Cambrian boundary samples by thiourea type chelate resin separation

A RNAA procedure is described for the determination of trace Ir in Precambrian-Cambrian boundary samples. After irradiation, the powdered sample is transferred to a graphite crucible to expel the massive silicon with mixed acid (HF–HCl–HNO₃) by heating. The residue is then fused with mixed fusion (Na₂O₂–NaOH) in a muffle furnace at 700°C for 15 minutes. After cooling, the fused mixture is leached with hot water. The final solution is adjusted to pH 1.5–2.0 and then passed through a column filled with thiourea type chelate resin. The resin absorbed with¹⁹²Ir is measured for 4000–10 000 s by means of SCORPIO-3000 multi-channel computer — Ge(Li) detector system. Experiments with radioactive tracer are carried aout for checking radiochemical separation yield. The accuracy and precision of the method are evaluated by the analysis of U.S. geological SRMs DTS-1 and AG-Bohor-1. The method is used for the determination of trace Ir in several sets of Precambrian-Cambrian boundary samples collected from Yunnan province in China and the Ir anomaly is observed.     

热裂解气相色谱质谱法分析聚合物中红磷

采用单击热裂解(PY)模式和逸出气体分析(EGA)程序升温两种热裂解模式对红磷样品进行定性分析,利用气相色谱分离技术对红磷进行分离,根据红磷的特征质谱31,62,93,124及特征丰度比,质谱法分析不同材料中的红磷含量。单击热裂解模式下,材质和添加剂有可能对红磷造成干扰,改进后的EGA热裂解模式能排除红磷检测中材质和添加剂的干扰,并采用改进后的EGA裂解程序测定自制阳性样品中红磷的含量。结果表明:通过优化裂解温度和气相色谱条件可以有效改善红磷的分析结果,红磷质量浓度在100~500 mg/kg范围内具有良好线性,加标回收率在90.7%~97.7%,相对标准偏差(RSD)为1.6%~2.3%,定量限为81.27 mg/kg。     

Study on thermal decomposition of polymers by evolved gas analysis using photoionization mass spectrometry (EGA-PIMS)

Photoionization mass spectrometry (PIMS) with vacuum ultraviolet (VUV) light source provides an efficient and fragmentation-free method for the soft ionization of gaseous compounds, in order to facilitate an understanding of thermal decomposition behavior and chemical composition of polymeric materials. The PIMS was applied to the evolved gas analysis (EGA) system equipped with a skimmer interface which is constituted based upon a jet separator principle between a vacuum MS chamber and an atmospheric sample chamber in a furnace. A photoionization source with a deuterium (D₂) lamp was closely installed to the vacuum ionization chamber of a mass spectrometer to improve the ionization efficiency. The thermal decomposition of typical polymers in inert gas atmosphere was investigated by the EGA-PIMS and the resulting PI mass spectrum was characterized satisfactorily by only the parent ions with no contribution as a result of fragmentation during the ionization. The results suggested that the EGA-PIMS was an especially powerful and desirable in situ thermal analysis method for polymeric materials which evolve organic gases simultaneously and concurrently. The combination of EGA equipped with skimmer interface with no change of evolved gaseous species and PIMS with fragmentation-free during the ionization is described briefly, and the effective results are presented by comparing with EGA using conventional electron impact ionization mass spectrometry.     

Synthetic macro-reference samples for the calibration of instruments in inorganic bulk analysis

Summary Basic considerations are discussed and conditions are described for the careful production of oxide macro-samples in the mass range of 200 to 750 g, starting from compounds of tested purity. Solid state reactions were performed at high temperatures. Compounds sensitive to heating were added after heat treatment in a way which ensured homogeneity. The uptake of CO₂/H₂O during manipulations was controlled. The homogeneity of the samples was investigated as well as the success of the experimental approach to their desired, nominal analysis. Even after only moderate mechanical homogenisation, nominal and experimental values were found to be identical (within the limits of repeatability of the test methods), provided compounds with a sufficiently small grain size and of high enough a purity were used. The results obtained on these samples showed that spending a greater analytical effort to achieve the desired analysis, was unnecessary. A thoroughly performed control analysis — e.g., by reconstitution of the sample portion — was sufficient to exclude erroneous production steps. Then the nominal analysis was used to establish the internal laboratory certificate.

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Synthetische Makroreferenz-Proben zur Eichung von Instrumenten für die anorganische Bulk-Analyse

     

Transformation-Governed Heating Techniques in Thermal Analysis I.

The author gives a detailed survey on thermogravimetric investigations under quasi-isothermal — quasi-isobaric conditions (Q-TG). According to the principle of the technique the heating of the sample is governed by the transformation itself according to the feed-back principle in a way that the transformations should take place at a strictly constant rate, slower by orders of magnitude than in the case of the conventional techniques. Due to this, the transformations take place under ideal conditions, near to physico-chemical requirements.Based on the obtained advantageous results further methods were elaborated, like thermo-dilatometry (Q-TD), evolved gas analysis (Q-EGA) and microdistillation under quasi-isothermal conditions.The second part of the present review deals with DTA and DSC techniques under quasi-isothermal conditions elaborated recentlyThis revised version was published online in November 2005 with corrections to the Cover Date.     

Hydrogenation of CO2 conjugated with dehydrogenation of cyclohexane over an intermetallic catalyst

Transformations of carbon dioxide catalyzed by the hydride form of [TiFe_0.95Zr_0.03Mo_0.02]H_x, by the industrial Pt/Al₂O₃ catalyst, and by a mixture of the above materials were studied. Study of the thermal desorption of H₂ showed the presence of two forms of absorbed hydrogen, namely, the weakly bound hydrogen, which is evolved from the intermetallic structure on heating to 430 °C under Ar, and the strongly bound hydrogen (SBH), which remains in the intermetallic compound at higher temperatures (up to 700 °C). In a carbon dioxide medium, the SBH enters into selective CO₂ reduction to give CO at 350—430 °C and 10—12 atm. The selectivity of the formation of CO reaches 80—99% for conversion of CO₂ between 50—70%, the SBH being consumed almost entirely for the reduction of CO₂. In the presence of the mixed catalyst, conjugate reactions proceed efficiently; dehydrogenation of cyclohexane yields hydrogen, which is consumed for CO₂ hydrogenation.     

New approach for the kinetic analysis of cellulose using EGA-MS

This paper describes a new approach for kinetic analysis based on evolved gas analysis-mass spectrometry (EGA-MS) using pyrolyzer-gas chromatography/MS (Py-GC/MS). The kinetic results derived by this model-free kinetic analysis using the EGA-MS thermograms of cellulose were comparable to those using thermogravimetric analysis (TGA). The activation energies were in the range of 149–194 kJ/mol (mean 169 kJ/mol) for EGA/MS and 152–181 kJ/mol (mean 165 kJ/mol) for TGA. This suggests that Py-GC/MS can be used not only for the qualitative analysis of pyrolyzates, but also for the kinetic analysis of pyrolysis.     

A novel direct coupling of simultaneous thermal analysis (STA) and Fourier transform-infrared (FT-IR) spectroscopy

Evolved gas analysis (EGA) from thermal analyzers such as thermogravimetry (TG) or simultaneous thermal analysis (STA) which refers to simultaneous TG–DSC is well established since it greatly enhances the value of TG or TG–DSC results. The sensitive and selective FT-IR technique is in particular useful for the analysis of organic molecules but also for infrared active permanent gases evolved during most decomposition processes. The coupling interface between thermal analyzers and FT-IR spectrometers usually consists of heated adapters and a flexible, heated transfer line. In this work, a novel direct coupling of an STA instrument and an FT-IR spectrometer without a transfer line is presented. A very small FT-IR spectrometer is directly mounted on top of the STA furnace leading to a compact and fully integrated STA–FT-IR coupling system. The possibilities and the value of simultaneous STA–FT-IR measurements are demonstrated for organic, biomass, and ceramic samples in the temperature range between room temperature and about 1,500 °C. Various samples from the field of inorganics and organics—especially polymers—were furthermore measured showing the advantages of the direct STA–FT-IR coupling compared to state-of-the-art STA–FT-IR coupling using a heated transfer line: we found that the time delay caused by the volume of the transfer line itself is rather negligible whereas a significantly better correlation between gas detection and TG results was observed in case of some highly condensable decomposition gases. Aspects of quantification of evolved gases are furthermore discussed as well as the known nonlinearity of FT-IR detection at higher gas concentrations.     

Hyphenation of thermogravimetry and soft single photon ionization–ion trap mass spectrometry (TG–SPI–ITMS) for evolved gas analysis

Thermal processes are part of many industrial treatments; therefore, it is of great interest to gain more insight of these processes. Evolved gas analysis (EGA) is the most straightforward way to make chemical reactions in thermal processes accessible for on-line investigations. The sample matrix of evolved off gas e.g., from coffee roasting is a permanently changing and complex mixture of a multitude of substances that have to be analyzed simultaneously for real on-line investigations without any sample trapping or separation device. Therefore, a measurement system as an ion trap mass spectrometer (ITMS) with soft ionization is required with its tandem mass spectrometry capability to provide distinct substance identification unperturbed by the remaining matrix. The presented novel system setup is based on a thermogravimetric device (TG) to simulate the thermal treatment as in industrial processes combined with an ITMS with soft single photon ionization (SPI) to achieve the required substance information. Hence it is possible to gain single mass spectrometric information of expected substances for process control. More comprehensive than that are the two-dimensional MS data which are required for research and process development purposes though. The conducted analyses show that this novel setup is able to provide distinct substance identification in evolved gas of roast and ground coffee powder. To our knowledge, this is the first TG–SPI–ITMS setup with successful application in verifying the identity of different mass traces within a single run.     

Laser pyrolysis of carbonaceous rocks

Flash pyrolysis on carbonaceous rocks is used to determine total carbon contents as well as the state of thermal maturation of specific samples. Short, intense heating greatly accelerates maturation-like processes. A series of radical fragments are generated leaving complex char residue. These volatile fragments quench into stable molecular species, influenced by the pyrolysis environment.Experiments are described that utilize pulsed laser heating on rock samples. This convenient technique requires minimum sample preparation and is readily automated. Intense laser pulses (2–10 J) generate an acetylene-rich plasma that interacts with the normally short-lived radical fragments. During the rapid quenching process, acetylene-tagged stable compounds are formed as a direct result of acetylene-radical combination processes. Analysis of these acetylenic derivatives by gas chromatography—mass spectrometry gives a unique interpretation of both the sediment and the maturation process.