Temperature Control Modes in Thermal Analysis

Now we can use several temperature control modes, i.e., the isothermal run including stepwise heating and cooling, constant rate heating (or cooling), temperature control for sample thermal history, sample controlled thermal analysis (SCTA or controlled-rate thermal analysis, CRTA), temperature jump, rate jump, temperature modulation and repeated temperature scanning. Their advantages and drawbacks are reviewed with some illustrative examples, especially for application to kinetic analysis. The combined use of these varieties of temperature control mode is recommended by showing examples. Temperature modulation and repeated temperature scanning are discussed in comparison with temperature modulated DSC, and common and analogous points are elucidated. In relation to this, the possibility that an imaginary part of overall reaction rate constant in complex reaction is postulated. Finally,these modes are classified and tabulated from two viewpoints and other possible modes are shown. This revised version was published online in July 2006 with corrections to the Cover Date.     

Calibration of a quenching and deformation differential dilatometer upon heating and cooling: Thermal expansion of Fe and Fe-Ni alloys

Dilatometry is a technique for precise measurement of thermal dilatation of materials during heating or cooling. A procedure has been presented for calibration of a differential dilatometer operating with electromagnetic heating for metallic specimens both upon heating and cooling as well as under uniaxial compressive and tensile loading. The dilation signal has been calibrated for both heating and cooling and for uniaxial loading (compressive and tensile) using platinum or iron reference specimens, for which recommended dilational data are available. The ferro- to paramagnetic transition (characterised by the Curie temperature) of pure iron or iron-based alloys has been adopted to calibrate the temperature in the dilatometric measurement under different loading modes during heating and cooling. On this basis calibrated data for the thermal expansion coefficients of Fe and Fe-Ni alloys have been obtained.     

Microscale temperature measurement by scanning thermal microscopy

Scanning thermal microscopy (SThM) can measure thermal image with a nano-scale spatial resolution. However, there remains an issue in quantitative temperature measurement. We proposed an active temperature measurement method that provides a real temperature image by compensating a variation in contact thermal conductance. Performance of the active method was examined by a multi-function cantilever made with micro-fabrication process. Response test of the cantilever showed about 50 Hz cut off frequency for both passive and active method. Temperature measurement test indicated that sensitivity of heat flow detection was not enough to measure real temperature regardless of the thermal contact conductance. Imaging test demonstrated that the active method takes temperature image closer to real temperature distribution than the passive method. This revised version was published online in August 2006 with corrections to the Cover Date.     

Data for the gas-liquid chromatographic analysis of essential oils. Determination of the composition of the essential oil of Marjoram

Summary By identification of the essential oil component ‘cis-sabinene hydrate acetate’ of marjoram we demonstrate that the mass spectrum—furnish to the chemical composition and molecular configuration of compounds—can lead to incorrect qualitative identification if retention data are not taken into consideration. We studied also the temperature-dependence of the retention data of different compounds, and our measurements showed that because of the different temperature-dependence, a change in the temperature of the analysis results in a change in order of elution. The use of this phenomenon, originating from the change of the retention data, both increases the safety of qualitative identification and aids determination of the optimum measurement conditions in both isothermal and temperature-programmed modes of operation. Presented at Balaton Symposium '01 on High-Performance Separation Methods, Siófok, Hungary, September 2–4, 2001     

Temperature and Heat Flow Calibration of A DSC-instrument in the Temperature Range Between −100 and 160°C

Thermoanalytical instruments are extensively used in R&D as well as in industrial quality control. A quantitative analysis of the data of a thermoanalytical measurement requires a careful calibration of the instrument. In differential scanning calorimetry (DSC) the quantities that have to be calibrated are the temperature and the heat flow. These two quantities are usually calibrated by evaluating melting or solid-solid transitions of some reference materials with well known transition enthalpies and temperatures. In this contribution we investigate temperature and heat flow calibration in the temperature range between −100 and 160°C. We included 9 different samples for the analysis and established some general rules for the calibration process. As a result we found that with a well calibrated instrument the heat flow can be measured with 90% confidence to about ± 3% accuracy in this temperature range. With respect to temperature calibration we find that accuracies of ±0.8°C (90% confidence) may be expected. These values represent general accuracy limitations of DSC’s due to varying heat transfer conditions within the samples. This revised version was published online in July 2006 with corrections to the Cover Date.     

A universal sample injection system for capillary column GC using a programmed temperature vaporizer (PTV)

This article describes the use of a programmed temperature vaporizer injection system which overcomes many of the classical problems associated with other injection techniques employed in capillary GC. The system can be operated in three distinct modes.     

基于SPECS生产的分子束外延设备样品加热平台的改进

改进了分子束外延设备样品加热平台的加热和测温方式,在原有热辐射加热和红外测温的基础上,增加直流电流加热并采用比例积分微分(PID)精密控温装置对样品加热台进行测温和控温.改进后,原有设备所能制备的研究样品范围更广,并且还增加了围绕设备所展开的科研方向,扩充了设备的使用范围.     

试验箱温、湿度校准装置的研制

介绍试验箱温、湿度校准装置的模型建立,温、湿度传感器的选择及软硬件构成,利用温、湿度精密测量,多路信号输入,单片机控制等功能,实现装置的温、湿度多点校准。通过验证试验证明该装置测量准确可靠。     

Vibrational averaging of the chemical shift in crystalline α‐glycine

Averaging of the chemical shift over the molecular motion improves the simulated data and provides additional information about the temperature dependence and system dynamics. However, crystal modeling is difficult due to the limited precision of the plane‐wave density functional theory (DFT) methods and approximate vibrational schemes. On the glycine example, we investigate how the averaging can be achieved within the periodic boundary conditions at the DFT level. The nuclear motion is modeled with the vibrational configuration interaction, with other simplified quantum anharmonic schemes, and the classical Born–Oppenheimer molecular dynamics (BOMD). The results confirm a large vibrational contribution to the isotropic shielding values. Both the first and second derivatives of the shielding were found important for the quantum averaging. The first derivatives influence the shielding mostly due to the anharmonic character of the CH and NH stretching modes, whereas second derivatives produce most vibrational corrections associated with the lower‐frequency vibrational modes. Temperature excitations of the lowest‐frequency vibrational states and the expansion of the crystal cell both determine the temperature dependence of nuclear magnetic resonance parameters. The vibrational quantum approach as well as classical BOMD schemes provided temperature dependencies of the chemical shifts that are consistent with the previous experimental data. © 2012 Wiley Periodicals, Inc.     

Application of near-infrared spectra on temperature-controlled protein crystallization

Large, high-quality protein crystals are required for the structural determination of proteins via X-ray diffraction. In this article, we propose a technique to facilitate the production of such crystals and validate its feasibility through simulations. An analytical method for protein aqueous solution based on a Fourier transform infrared (FTIR) spectroscopy is combined with a temperature control strategy to manipulate the extent of supersaturation during crystal growth, thus impacting crystal quality. The technique requires minimal knowledge about the growth kinetics a priori. The simulations show that, under ideal conditions, the design can be as effective as predesigned temperature programs for crystallization based on known growth kinetics. Two kinds of errors might be encountered with this design. Error in the estimated number of seed crystals can result in a growth rate deviating from the desired one. Nevertheless, the deviation is usually tolerable and system instability is unlikely to occur. Based on the standard error of our FTIR method, errors in concentration measurement are simulated. Measurement error can result in system instability and impair the control algorithm. Such errors may be compensated by limiting the temperature change taken by the control action, or by improving the measurement precision through the use of regressed concentrations. Through simulations, it is shown that the proposed design is practical and represents a significant improvement over the commonly used isothermal crystallization technique.     

Mathematical Modeling of Multicomponent Nonisothermal Adsorption in Sorbent Particles Under Pressure Swing Conditions

A detailed model for nonisothermal sorption of multicomponent mixtures in a single sorbent particle (monodisperse or bidisperse with negligible intracrystalline mass transport limitations) under pressure swing conditions is developed in this study. The dusty-gas model is used to describe the coupling of the molar fluxes, the temperature, the partial pressures and the partial pressure gradients of the components in the pore space of the particle. The variations of the temperature are described by an energy equation in which both convective and conductive modes of heat transport are accounted for. No limitations are imposed on the number of the components in the mixture and on the type of the adsorption isotherm. The model is applied in the investigation of the industrially important air-zeolite 5A system. Two cases with respect to the surrounding gas phase are examined: infinite environment, which is representative for single particle experiments, and finite environment, which is representative for the situation in packed bed adsorbers. It is found that in an infinite environment the external and internal temperature gradients are equally important while in a finite environment the external heat transport limitations are negligible. It is concluded that in modeling the nonisothermal operation of adsorption processes occurring in packed beds it is not necessary to allow for the temperature differences between the gas phase and the surface of the adsorbing particles. Furthermore, if the temperature gradients within the particles can be neglected, only a single temperature equation is needed to describe the energy transport in the bed.     

Field measurement of the organic peroxy radicals by the low-pressure reactor plus laser-induced fluorescence spectroscopy

A low-pressure reactor (LPR) was developed for the measurement of ambient organic peroxy (RO₂) radicals with the use of the laser-induced fluorescence (LIF) instrument. The reactor converts all the RO_x (= RO₂ + HO₂ + RO + OH) radicals into HO₂ radicals. It can conduct different measurement modes through altering the reagent gases, achieving the speciated measurement of RO₂ and RO₂^# (RO₂ radicals derived from the long-chain alkane, alkene and aromatic hydrocarbon). An example of field measurement results was given, with a maximum concentration of 1.88 × 10⁸ molecule/cm³ for RO₂ and 1.18 × 10⁸ molecule/cm³ for RO₂^#. Also, this instrument quantifies the local ozone production rates directly, which can help to deduce the regional ozone control strategy from an experimental perspective. The new device can serve as a potent tool for both the exploration of frontier chemistry and the diagnosis of the control strategies.     

An empirical model to predict temperature‐dependent thermal conductivity of amorphous polymers

Thermal conductivity in polymers has been theoretically and experimentally studied in good detail, but there is a need for more accurate models. Polymeric thermal conductivity exhibits a plateau‐like transition at temperatures around 10 K, which is not well accounted for by existing models. In this work, an empirical model that can predict temperature‐dependent thermal conductivity of amorphous polymers is developed. The model is based on kinetic theory and accounts for three sets of vibrational modes in polymers, and is developed using classical expressions, results of previous simulations, and experimental data. Fundamental material properties like density, monomer molecular weight, and speed of sound are the only input parameters. The model provides estimates for the locations of transitions between different sets of vibrational modes, an upper limit for the thermal conductivity, and temperature‐dependent thermal conductivity, which are in good agreement with experimental data. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 1160–1170     

Phoxonic crystals—a new platform for chemical and biochemical sensors

A new sensor platform is based on so-called phoxonic crystals. Phoxonic crystals are structures designed for simultaneous control of photon and phonon propagation and interaction. They are characterized by a periodic spatial modulation of the dielectric constant as well as elastic properties on a common wavelength scale. Multiple scattering of photons and phonons results in a band gap where propagation of both waves is prohibited. The existence of photonic and phononic band gaps opens up opportunities for novel devices and functional materials. The usage of defect modes is an advantageous concept for measurement. The defect also acts as point of measurement. We show theoretically that the properties of the defect mode can be tailored to provide very high sensitivity to optical and acoustic properties of matter confined within a defect cavity or surrounding the defect or being adsorbed at the cavity surface. In this paper, we introduce the sensor platform and analyze the key features of the sensor transduction scheme. Experimental investigations using a macroscopic device support the theoretical findings.     

Comparison of different injection modes in edible oil minor components analysis

Waxes and fatty acid alkyl esters are minor components used as official parameters to control the authenticity and quality of a high‐value olive oil product. A poor measurement can lead to a misleading classification of the oil. The official method requires their analysis together by capillary gas chromatography equipped with a flame ionization detector and an on‐column injector to avoid discrimination and thermal degradation. The degradation can occur to a different extent if different (and not properly optimized) injectors are used. However, other injection techniques, such as programmed‐temperature vaporizer, are much more versatile and more widespread. The aim of the present work was to compare the performance of a programmed‐temperature vaporizer injector, in on‐column and splitless mode, with the on‐column injector to analyze alkyl esters and waxes. Discrimination among high‐boiling compounds was evaluated, as well as the occurrence of thermal degradation, especially of sterols and diterpene alcohol (phytyl and geranylgeraniol) esters. A proper optimization of a programmed‐temperature vaporizer injection, with particular attention to the liner selection, was proven to provide comparable results to the traditional on‐column injection. A performance comparison was carried out both on standard mixtures and on real oil samples.     

Advanced sedex ( nsitive etector of othermic processes)

The instrument described is suitable for the investigation of the thermal behaviour of substances and reaction mixtures under production conformable conditions; this is made possible by the sophisticated design of the sample chamber: easy stirring of the samples, measuring under any gas atmosphere and while bubbling gas through the sample, choice of the sample container and visual observation during the measurement. The control device allows the choice of one of three operational modes: constant temperature, linear increase in temperature, and adiabatic control; this permits the application of the SEDEX apparatus for a variety of methods including dynamic scanning, isoperibolic measurements, and (quasi) adiabatic studies.     

Advanced sedex (sensitive detector of exothermic processes)

The instrument described is suitable for the investigation of the thermal behaviour of substances and reaction mixtures under production conformable conditions; this is made possible by the sophisticated design of the sample chamber: easy stirring of the samples, measuring under any gas atmosphere and while bubbling gas through the sample, choice of the sample container and visual observation during the measurement. The control device allows the choice of one of three operational modes: constant temperature, linear increase in temperature, and adiabatic control; this permits the application of the SEDEX apparatus for a variety of methods including dynamic scanning, isoperibolic measurements, and (quasi) adiabatic studies.     

Injection temperature effects using On-column and split sampling in capillary gas chromatography

The effect of sample injection temperature on quantitation is examined for on-column and conventional split modes of sampling in capillary gas chromatography. Discrimination effects can be observed even with on-column injection if the injection temperature is too far above the boiling point of the solvent (or that of a major low boiling constituent(. This is attributed to higher boiling components being left behind in the syringe needle, and a set of simulation experiments are described to illustrate this effect. Various discrimination patterns using conventional split injection were observed, depending on temperature of injection. Apart from syringe needle effects, discrimination is probably due to the preferential venting of higher boiling components as liquid sample droplets, which can have a lifetime greater than the time of transit to the splitter. With such a two-phase system, involving variable droplet size, the flow distribution in the splitter will be critical to uniform sampling. The use of combination on-column/split sampling, with the appropriate temperature control to provide sample uniformity to the splitter is discussed as an advantageous alternative to conventional split sampling.     

Instrumental correction of time dependent counting losses in high rate gamma-ray spectrometry

A CAMAC system was installed for pulse height analysis and correction of counting losses due to the dead-time of a multichannel analyzer and the pulse pile-up. A computer program was developed to control the whole system, and to collect and store data in both conventional and cyclic measurement modes.     

Torsion pendulum automation by a single microcomputer

A new automated torsional pendulum is described. It uses a single photocell for the measurement of the period of oscillation and the logarithmic decrement. Data acquisition, data processing and temperature control are all performed by a single microcomputer. The result is that the instrument can be produced and operated more cheaply than before.The principles behind the design, the method of determining the shape factor, the calibration procedure and the software are discussed. Examples are given to illustrate the use of this instrument. A practical limitation is that the loss tangent should not exceed about 3.