Comprehensive two-dimensional gas chromatographic separations with a microfabricated thermal modulator

Rapid, comprehensive two-dimensional gas chromatographic (GC × GC) separations by use of a microfabricated midpoint thermal modulator (μTM) are demonstrated, and the effects of various μTM design and operating parameters on performance are characterized. The two-stage μTM chip consists of two interconnected spiral etched-Si microchannels (4.2 and 2.8 cm long) with a cross section of 250 × 140 μm(2), an anodically bonded Pyrex cap, and a cross-linked wall coating of poly(dimethylsiloxane) (PDMS). Integrated heaters provide rapid, sequential heating of each μTM stage, while a proximate, underlying thermoelectric cooler provides continual cooling. The first-dimension column used for GC × GC separations was a 6 m long, 250 μm i.d. capillary with a PDMS stationary phase, and the second-dimension column was a 0.5 m long, 100 μm i.d. capillary with a poly(ethylene glycol) phase. Using sets of five to seven volatile test compounds (boiling point ≤174 °C), the effects of the minimum (T(min)) and maximum (T(max)) modulation temperature, stage heating lag/offset (O(s)), modulation period (P(M)), and volumetric flow rate (F) on the quality of the separations were evaluated with respect to several performance metrics. Best results were obtained with a T(min) = -20 °C, T(max) = 210 °C, O(s) = 600 ms, P(M) = 6 s, and F = 0.9 mL/min. Replicate modulated peak areas and retention times were reproducible to <5%. A structured nine-component GC × GC chromatogram was produced, and a 21 component separation was achieved in <3 min. The potential for creating portable μGC × μGC systems is discussed.     

Thermogravimetry-evolved gas analysis-mass spectrometry system for materials research

Thermal analysis is a widely used analytical technique for materials research. However, thermal analysis with simultaneous evolved gas analysis describes the thermal event more precisely and completely. Among various gas analytical techniques, mass spectrometry has many advantages. Hence, an ultra high vacuum (UHV) compatible mass spectrometry based evolved gas analysis (EGA-MS) system has been developed. This system consists of a measurement chamber housing a mass spectrometer, spinning rotor gauge and vacuum gauges coupled to a high vacuum, high temperature reaction chamber. A commercial thermogravimetric analyser (TGA: TG + DTA) is interfaced to it. Additional mass flow based gas/vapour delivery system and calibration gas inlets have been added to make it a versatile TGA-EGA-MS facility. This system which gives complete information on weight change, heat change, nature and content of evolved gases is being used for (i) temperature programmed decomposition (TPD), (ii) synthesis of nanocrystalline materials, (iii) gas-solid interactions and (iv) analysis of gas mixtures. The TPD of various inorganic oxyanion solids are studied and reaction intermediates/products are analysed off-line. The dynamic operating conditions are found to yield nanocrystalline products in many cases. This paper essentially describes design features involved in coupling the existing EGA-MS system to TGA, associated fluid handling systems, the system calibration procedures and results on temperature programmed decomposition. In addition, synthesis of a few nanocrystalline oxides by vacuum thermal decomposition, gas analysis and potential use of this facility as controlled atmosphere exposure facility for studying gas-solid interactions are also described.     

Incorporation of single-wall carbon nanotubes into an organic polymer monolithic stationary phase for mu-HPLC and capillary electrochromatography

Single-wall carbon nanotubes (SWNT) were incorporated into an organic polymer monolith containing vinylbenzyl chloride (VBC) and ethylene dimethacrylate (EDMA) to form a novel monolithic stationary phase for high-performance liquid chromatography (HPLC) and capillary electrochromatography (CEC). The retention behavior of neutral compounds on this poly(VBC-EDMA-SWNT) monolith was examined by separating a mixture of small organic molecules using micro-HPLC. The result indicated that incorporation of SWNT enhanced chromatographic retention of small neutral molecules in reversed-phase HPLC presumably because of their strongly hydrophobic characteristics. The stationary phase was formed inside a fused-silica capillary whose lumen was coated with covalently bound polyethyleneimine (PEI). The annular electroosmotic flow (EOF) generated by the PEI coating allowed peptide separation by CEC in the counterdirectional mode. Comparison of peptide separations on poly(VBC-EDMA-SWNT) and on poly(VBC-EDMA) with annular EOF generation revealed that the incorporation of SWNT into the monolithic stationary phase improved peak efficiency and influenced chromatographic retention. The structures of pretreated SWNT and poly(VBC-EDMA-SWNT) monolith were examined by high-resolution transmission electron microscopy, Raman spectroscopy, scanning electron microscopy, and multipoint BET nitrogen adsorption/desorption.     

含新型发色团的非线性光学聚合物体系的热性能研究

分别对掺杂了新型发色团分子的聚甲基丙烯酸甲酯(PMMA)和纯的PMMA进行了热重分析,得到了2种体系在不同质量损失下的温度并计算了积分程序分解温度(IPDT).结果表明,掺杂后聚合物体系的热稳定性好于纯的PMMA.采用Achar方法和Coats-Redfern方法对2种体系热降解的动力学过程进行了分析,得到了对应的非等温动力学方程.     

Effect of Decomposition Kinetics of Titanium Hydride on the Al Alloy Melt Foaming Process

The gas released from the titanium hydride decomposition is one of the key factors to influence the Al alloy melt foaming process.In this study,a set of decomposition kinetic equations of titanium hydride was acquired by separating its temperature programmed decomposition(TPD) spectrum,which was acquired by a special designed TPD apparatus with argon used as carrier gas and thermal conductivity cell as the detector.According to these equations,the decomposition and hydrogen release characteristics of titanium hydride at a fixed/elevated temperature are described quantitatively,which can be applied to forecast the Al alloy melt foaming process and furnish the theoretical basis for fabrication of three-dimensional complex shaped Al alloy foam.     

Helical sorbent microtrap for continuous sampling by a membrane and trap interface for on-line gas chromatographic monitoring of volatile organic compounds

A helical sorbent microtrap consisting of a helical sorbent fixed inside a silicosteel capillary tube is presented. The main parameters that affect the safe sampling time of the helical sorbent microtrap in continuous sampling by a membrane and trap interface for on-line gas chromatographic monitoring of organic volatiles in gaseous samples are examined, taking into account the helical configuration of the sorbent, the presence of the membrane in system, and the properties of the analytes. Thermal desorption of analytes from the helical sorbent trap was also examined having regard to the influence of the turbulent flow generated by the helical sorbent in the heat transfer and the effect of thermal backward flow on the peak shape. The practical application of the helical sorbent microtrap in a membrane and trap interface was demonstrated by on-line gas chromatographic monitoring of four volatile organic compounds in the fume hood air and of volatile organic compounds from a diesel engine exhaust. The limit of detection was in the picogram per milliliter range, depending on the time of trapping and the parameters that affect the permeation through the membrane.     

The interaction between PTFE and porous metals and metal blacks — rheological characterization and thermal degradation of the polymer

High molecular weight PTFE (¯M _n=10⁴ to 10⁶) normally exhibits high thermal stability and melt viscosity. When contacted by high surface area metal blacks (Au or Pt) or porous sintered metals (Au or Ni) and heated near the melting temperature, the effective viscosities and thermal stabilities of the PTFE are orders of magnitude lower than those normally exhibited by the polymer. These results are discussed in terms of capillary flow, heterogeneous catalytic degradation, and the diffusion controlled evolution of volatile decomposition products.     

Thermal decomposition of miscible phenoxy/poly(ethylene oxide) blends

The thermal decomposition of miscible blends composed by the poly(hydroxy ether of bis-phenol A) (phenoxy) and poly(ethylene oxide) (PEO) has been investigated by dynamic thermogravimetric analysis. The results obtained indicate that the blend composition affects the thermal decomposition processes. In general it can be seen that phenoxy causes a negative effect on the thermal stability of the blends.     

Helical sorbent for fast sorption and desorption in solid-phase microextraction-gas chromatographic analysis

A new technique for solid-phase microextraction (SPME) of analytes using a helical solid sorbent followed by thermal desorption into a gas chromatographic injector is reported. The main factors that affect the mass transport of analytes in sorption and thermal desorption process using a poly(dimethylsiloxane) (PDMS) helical sorbent are described. The sorption and thermal desorption were achieved in a few seconds, being very close by the theoretical prediction. Both processes were very fast by the reduction of the thickness of boundary layer between sorbent and gaseous sample as a result of a turbulent rotational flow of the headspace air on the surface of sorbent, which is generated by the helical configuration of the sorbent. The thermal desorption was also reduced by improving heat transfer into a thin boundary layer and by increasing the temperature of the heat transporter (carrier gas). The sorption and desorption with PDMS helical sorbent were compared with those of the PDMS silica rod. The extraction time was as much as 15 times faster with the PDMS helical sorbent than with the PDMS silica rod. The desorption with the PDMS helical sorbent was very fast, giving narrow peaks without tailing and a high efficiency of separation in comparison with PDMS silica rod.     

Spectroscopic and thermal behavior of ZnHg(SCN)4

The synthesis and purification of zinc mercury thiocyanate, ZnHg(SCN)₄ (ZMTC), are described. The identity of the synthesized compound was characterized by elemental analysis, X-ray powder diffraction, infrared, Raman, and UV/Vis/NIR transmission spectra. The thermal stability and thermal decomposition of ZMTC crystal were investigated by means of thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) measurements. The intermediates and final products of the thermal decomposition were identified by X-ray powder diffraction (XRPD).     

Chiral monolithic columns for enantioselective capillary electrochromatography prepared by copolymerization of a monomer with quinidine functionality. 2. Effect of chromatographic conditions on the chiral separations

The effect of chromatographic conditions on the performance of chiral monolithic poly(O-[2-(methacryloyloxy)-ethylcarbamoyl]-10,11-dihydroqui nidine-co-ethylene dimethacrylate-co-2-hydroxyethyl methacrylate) columns in the capillary electrochromatography of enantiomers has been studied. The flow velocity was found to be proportional to the pore size of the monolith and both the pH and the composition of the mobile phase. The length of both open and monolithic segments of the capillary column was found to exert a substantial effect on the run times. The use of monoliths as short as 8.5 cm and the "short-end" injection technique enabled the separations to be achieved in approximately 5 min despite the high retentitivity of the quinidine selector. Very high column efficiencies of close to 250000 plates/m and good selectivities were achieved for the separations of numerous enantiomers using the chiral monolithic capillaries with the optimized chromatographic conditions.     

Thermal decomposition of ferric and ammonium sulphates obtained by bio-oxidation of water pickling liquors with Thiobacillus ferrooxidans

Sulphuric water pickling liquor containing ferrous sulphates was oxidized by Thiobacillus ferrooxidans at different pHs. The oxidized solution was then evaporated and crystallized, and products characterized by X-ray powder diffraction, X-ray high temperature powder diffraction and Fourier transform infrared (FTIR) spectrometry. The thermal decomposition of these materials, studied by calorimetric and thermogravimetric techniques, shows that iron(III) hydroxysalts and monoammonium and triammonium salts are formed during the oxidation-evaporation-crystallization process. However, this formation depends upon pH.     

Polymer-coated fibrous materials as the stationary phase in packed capillary gas chromatography

Synthetic polymer filaments have been introduced as the support material in packed capillary gas chromatography (GC). The filaments of the heat-resistant polymers, Zylon, Kevlar, Nomex, and Technora, were longitudinally packed into a short fused-silica capillary, followed by the conventional coating process for open-tubular GC columns. The separation of several test mixtures such as n-alkylbenzenes and n-alkanes was carried out with these polymer-coated fiber-packed capillary columns. With the coating by various polymeric materials on the surface of these filaments, the retentivity was significantly improved over the parent fiber-packed column (without polymer coating) as well as a conventional open-tubular capillary of the same length. The results demonstrated a good combination of Zylon as the support and poly(dimethylsiloxane)-based materials as the coating liquid-phase for the successful GC separation of n-alkanes and polycyclic aromatic hydrocarbons (PAHs), while successful applications for other separations such as poly(ethylene glycol) coating for the separation of alcohols were also obtained. From the results it has been suggested that the selectivity of the fiber-packed column could be tuned by selecting different coating materials, indicating the promising possibility for a novel usage of fine fibrous polymers as the support material that can be combined with newly synthesized coating materials specially designed for particular separations. Taking advantage of good thermal stability of the fibers, the column temperature could be elevated to higher than 350 degrees C with the combination of a short metallic capillary.     

Plasma pre-treatment of liquid crystal polymer and subsequent metallization by PVD

In this paper surface modification of a liquid crystal polymer (LCP) substrate by oxygen containing plasma pre-treatment and subsequent Cu/Cr deposition by physical vapour deposition (PVD) technique is described. By pre-treatment with oxygen containing plasma more volatile reaction products are generated compared to argon plasma pre-treatment as is shown by the etching rate. The small molecule fragments generated during the pre-treatment process are analyzed by mass spectrometry. After the pre-treatment metal layers with suitable adhesion strength even after 1000 cycles of thermal shock are obtained.     

One-step synthesis and flame retardancy of sheaf-like microcrystal antimony oxychloride

A mild and facile solution route has been developed for large-scale synthesis of sheaf-like antimony oxychloride Sb8O11CI2 (H2O)6 microcrystal at room temperature. The morphologies and structures of the as-prepared products were characterized by X-ray powder diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). A mechanism for the formation of the sheaf-like microstructure was tentatively proposed. The shape regulation was attributed to the capping mode of the PVP-directed antimony oxychloride crystal. The thermogravimetric and differential thermal analysis (TG/DTA) were employed to investigate thermal decomposition mechanism and temperature-dependent phase transition of antimony oxychloride Sb8O11CI2 (H2O)6 in the air. The flammable property determined by the cone calorimeter showed excellent flame retardancy when applied this antimony oxychloride in poly (vinyl chloride) (PVC) polymer.     

Thermal degradation of poly(3-hydroxybutyrate) and poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) in nitrogen and oxygen studied by thermogravimetric-Fourier transform infrared spectroscopy

The thermal degradation behavior of poly(3-hydroxybutyrate) (PHB) and poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (P(HB-co-HHx), HHx=12 mol%) has been studied under different environmental conditions by thermogravimetric analysis (TGA) Fourier transform infrared (FT-IR) spectroscopy. It is reported that at higher temperature (>400 degrees C) carbon dioxide and propene are formed from the decomposition product crotonic acid in a nitrogen atmosphere, whereas in an oxygen atmosphere propene oxidizes in a further step to carbon dioxide, carbon monoxide and hydrogen. It was also found that PHB and P(HB-co-HHx) have a similar thermal degradation mechanism. The analysis of the FT-IR-spectroscopic data was performed with 2D and perturbation-correlation moving-window 2D (PCMW2D) correlation spectroscopy.     

Thermal decomposition and micropore formation in PEK,PEEK and PES

At strain rates greater than about 10 the deformation of polymers is an adiabatic process which can lead to the generation of very high localized temperatures. These may be well in excess of the temperatures required for thermal decomposition of the polymer to occur. It is speculated that gaseous products arising from such decomposition may act as the source of microcavities and craze initiators. Experiments are described in which the thermal decomposition reaction parameters of polyetherketone, polyetheretherketone, and polysulphone are measured using differential scanning calorimetry and thermogravimetric analysis, and the decomposition products analysed by mass spectrometry. The results indicate that the proposed mechanism could act as a source of micropores with total pore volumes amounting to several per cent of the material volume.     

聚碳酸亚环己酯的热分解性能及动力学

研究了聚碳酸亚环己酯(二氧化碳-氧化环己烯共聚物,简称PCHC)的非等温热分解行为的影响因素,并对热分解反应动力学及机理进行了研究。结果表明,碳酸酯键含量和升温速率等都对PCHC的热分解行为有较大影响;高交替度的PCHC在350℃左右完全分解,不残留炭黑,具有优良的热分解性能。用Flynn-Wall-Ozawa和Kinssinger两种方法求得PCHC的热分解反应的表观活化能分别为144.51kJ/mol和143.23kJ/mol。并结合Coats-Redfern方法证明了PCHC的热分解为随机核化机理。     

主链含苯基均三嗪联苯型聚芳醚的热稳定性

利用热重分析(TG、DTG)研究了主链含苯基均三嗪联苯型聚芳醚在不同气氛和升温速率时的热降解动力学。比较了升温速率和气体气氛对热降解行为的影响,结果表明,该聚合物具有优异的耐热性和耐热氧化稳定性。用Flynn-Wall-Ozawa,Freeman-carroll等方法进行了动力学处理,计算得热降解反应活化能分别为291.19kJ/mol,286.83kJ/mol,与Kissinger法计算活化能值283.25kJ/mol非常接近。结合Coats-Redfern方法,推测出聚合物在氮气气氛中的热分解机理为F2机理,其机理函数积分式为g(α)=1/(1-α)。     

Predicting gas chromatographic separation and stationary-phase selectivity using computer modeling

A computer modeling technique has been developed which allows for the prediction of chromatographic separation and stationary-phase selectivity. This technique enables development of application-specific gas chromatographic columns by allowing for the simultaneous optimization of physical dimensions, flow and temperature programs, and stationary-phase composition. Stationary-phase selectivity is the most powerful tool available to achieve a separation; however most commercially available columns were not designed to have a selectivity specific to the separations for which they are used. The techniques described in this paper were developed to address this need.