The temperature calibration on cooling of thermal analysis instruments is important for the accurate study of the non-isothermal crystallization kinetics of semi-crystalline polymers. In previous works, a methodology was proposed for performing the calibration on cooling of differential scanning calorimeters (DSCs) with standard metals, and the calibration errors were checked using transitions of high-purity liquid crystals. In this work, alternative, physically meaningful, procedures for carrying out the calibration on cooling are analyzed and validated. The calibration errors are evaluated also with liquid crystalline transitions, when the calibration is performed with standard metals, in a wide temperature range, and when due account is taken for the need of isothermal corrections to the temperature measurements. It is shown that any pair of standard metals may be used to calibrate on cooling, that the calibration errors increase for wider working temperature ranges and that, providing that certain conditions are fulfilled, both calibration procedures yield similar results. 相似文献
A new approximate formula for temperature integral is proposed. The linear dependence of the new fomula on x has been established. Combining this linear dependence and integration-by-parts, new equation for the evaluation of kinetic
parameters has been obtained from the above dependence. The validity of this equation has been tested with data from numerical
calculating. And its deviation from the values calculated by Simpson's numerical integrating was discussed. Compared with
several published approximate formulae, this new one is much superior to all other approximations and is the most suitable
solution for the evaluation of kinetic parameters from TG experiments.
This revised version was published online in August 2006 with corrections to the Cover Date. 相似文献
A new method for inductively coupled plasma atomic emission spectrometry (ICP-AES) determination of trace Sc and Y, based on gaseous compound introduction into the plasma as their thenoyltrifluoroacetone (TTA) complexes by electrothermal vaporization was developed. Using the reagent TTA as chemical modifier can not only enhance the analytical signals, but also reduce the vaporization temperature. At a temperature of 1,000 °C the trace Sc and Y can be vaporized completely into ICP. The factors affecting the formation of the chelate and its vaporization behavior, such as drying time, vaporization temperature/time, reaction medium and the amount of TTA, were investigated in detail. Under the optimized conditions (drying temperature/time 100 °C/10 s, vaporization temperature/time 1,000 °C/4 s), the limits of detection for Sc and Y were 19 pg and 34 pg (3), respectively, and the relative standard deviations for Sc and Y were 4.2% (cSc=0.2 g mL–1; n=7) and 2.6% (cY=0.5 g mL–1; n=7). The linear ranges of the calibration graphs cover three orders of magnitude. The method was applied to the analysis of the biological reference materials (GBW 07602, bush branches and leaves; GBW 07604, poplar leaves), and the results obtained were in good agreement with the certified values. 相似文献
This paper presents results concerning structure and electrochemical characteristics of the La0.67Mg0.33 (Ni0.8Co0.1Mn0.1)x (x=2.5–5.0) alloy. It can be found from the result of the Rietveld analyses that the structures of the alloys change obviously
with increasing x from 2.5 to 5.0. The main phase of the alloys with x=2.5–3.5 is LaMg2Ni9 phase with a PuNi3-type rhombohedral structure, but the main phase of the alloys with x=4.0–5.0 is LaNi5phase with a CaCu5-type hexagonal structure. Furthermore, the phase ratio, lattice parameter and cell volume of the LaMg2Ni9phase and the LaNi5 phase change with increasing x. The electrochemical studies show that the maximum discharge capacity increases from 214.7 mAh/g
(x=2.5) to 391.1 mAh/g (x=3.5) and then decreases to 238.5 mAh/g (x=5.0). As the discharge current density is 1,200 mA/g, the high rate dischargeability (HRD) increases from 51.1% (x=2.5) to 83.7% (x=3.5) and then decreases to 71.6% (x=5.0). Moreover, the exchange current density (I0) of the alloy electrodes first increases and then decrease with increasing x from 2.5 to 5.0, which is consistent with the variation of the HRD. The cell volume reduces with increasing x in the alloys, which is detrimental to hydrogen diffusion and accordingly decreases the low-temperature dischargeability
of the alloy electrodes. 相似文献
A unique process of chemical oxidation polymerization of aniline using manganese dioxide (MnO2) as the oxidizing agent in an aqueous medium is described. The reaction between aniline and MnO2 follows a mechanism by which the organic monomer is oxidized while the metal oxide undergoes reductive dissolution. The effects of the amount of oxidizing agent and aniline, pH and temperature of the reactive system, type of acid on the yield and conductivity of polyaniline are discussed. The resulting polyaniline was characterized by [R and UV-Vis spectrometry. Polyaniline with a conductivity of 12.5 S/cm was obtained using 0.033 tool of aniline oxidized by 0.023 tool MnO2 in the presence of 100 mL of 2.7 mol/L HCI at 25℃ for 4 h. 相似文献
Luminescent particles of lead carboxymethyl cellulose (Pb(CMC)2) containing salicyl fluorones (THBF), Pb(CMC)2-THBF were synthesized by the sol-gel method, using sodium carboxymethyl cellulose (NaCMC) as precursor and Pb2+ as precipitant. Pb(CMC)2-THBF can emit the intense and stable solid substrate room temperature phosphorescence (SS-RTP) on filter paper. And EDTA can chelate Pb2+ in Pb(CMC)2-THBF, causing it to decompose into aqueous soluble components PbY2-, CMC- and THBF, which can react with Ag+ to form Ag(CMC)2-THBF, causing the decrease of phosphorescence intensity. Based on the facts above, a new method for the determination of trace silver by SS-RTP quenching method was established. The linear range of this method is 8.0-40.0 fg spot(-1) (20.0-100.0 pg ml(-1)), with a detection limit (LD) of 2.2 fg spot(-1) (corresponding to a concentration range of 5.5 x 10(-13) g ml(-1)), and the regression equation of working curve is DeltaI(p) = 12.56 + 0.5527C(Ag+) (fg spot(-1), 0.4 microl spot(-1)), n = 8, r = 0.9992. This method has been applied to the determination of trace silver in human hair and tea sample with satisfactory results. The mechanism of SS-RTP emission is also discussed. 相似文献
The crystal structure of Nd[Fe(CN)6]·4H2O has been refined by Rietveld analysis using high resolution synchrotron powder X-ray diffraction data. It belonged to the orthorhombic crystal system, Cmcm space group, with cell parameters: , and . The change in space group from P63/m which is observed in the pentahydrates (LnFe(CN)6·5H2O) to Cmcm in the tetrahydrates has been analyzed to be a consequence of the change in 9-fold coordination of Nd3+ in the pentahydrates to 8-fold coordination in the tetrahydrates, which changes the Nd3+ environment from tricapped trigonal prism to a distorted tricapped trigonal prism or square antiprism. Its decomposition process in air to produce NdFeO3 has been followed by thermogravimetric and differential thermal analysis, IR spectroscopy and laboratory powder XRD. We found that it is possible to synthesize crystalline NdFeO3 at temperatures as low as 380 °C and refine the structure of single phase crystalline NdFeO3 synthesized by this method at 600 °C. 相似文献
Thermal analysis of poly-methylmethacrylate (PMMA) impregnated porous gel silica glasses confirms that the PMMA chains form hydrogen bonds with the pore surface silanol groups. The adopted conditions for the insitu polymerisation result in about 4% of residual monomers trapped in the polymer, most of them in the amorphous structure. The polymer and monomer mixture takes up the whole of the free pore volume. Most of the residual monomer polymerises during the DSC scans above the glass transition temperature providing an excellent probe for the weak glass transition. Polymerisation in the gel silica glass medium affects the glass transition temperature, the length of polymer chains, and the degree of polymerisation. 相似文献
Recent developments in trapping efficiency inside ion trap mass spectrometer permitted to lower instrument detection limit (IDL). An IDL of 200 fg μl−1 injected with a signal-to-noise ratio of 5:1 for tetrachlorodibenzo-p-dioxin (TCDD) was obtained by gas chromatography coupled to a quadrupole ion storage mass spectrometer in tandem mode (GC/MS/MS). Coupling large volume programmable temperature vaporizer (PTV-LV) injection to GC/MS/MS provides an alternative and complementary method to classical splitless-GC injection connected to high-resolution mass spectrometry (splitless-GC/HRMS) method for dioxin monitoring in food and feed.
An injection volume of 10 μl was found to be the best compromise between the sensitivity requirements and the robustness required for a high throughput method. PTV-LV-GC/MS/MS and Splitless-GC/HRMS were compared by performing analysis on five different matrices such as beef fat, yolk eggs, milk powder, animal feed and serum samples covering a concentration range of two orders of magnitude (i.e. 0.2–25 ng WHO-TEQ kg−1). An analysis of variance (ANOVA) was carried out. Fisher tests pointed out that the method effect for all the 2,3,7,8 congeners was not significant, indicating that the null hypothesis (H0: μ1=μ2=…=μn) was not rejected. Moreover, the interaction effects between methods and matrices were not significant for most of the 2,3,7,8 congeners. However, three congeners (2,3,7,8-TCDF; 1,2,3,4,7,8-HxCDD and 1,2,3,4,6,7,8-HpCDD) were characterized by P-values lower than the significance level (=0.05). In toxic equivalence (TEQ), the study showed that no significant bias was observed between the two methods. Consequently, PTV-LV-GC/MS/MS is an attractive technique and can be used as a cost effective complementary method to HRMS for dioxin levels monitoring in food and feed. 相似文献