Chip calorimetry for fast cooling and thin films: a review

Here we review on the thin-film chip calorimeter with controllable cooling as well as heating rates up to 10⁶ K·s⁻¹ developed in the last 5 years at the Institute of Physics, Rostock University. The calorimeter has been successfully used for fast thermal processing and simultaneous calorimetric measurements of many polymer samples, the physical properties of which are generally dependent strongly on their thermal history. Besides, owing to the very small addenda heat capacity, the calorimeter is very sensitive to study samples of only several tenths of nanograms. With differential alternating current (AC) design, the sensitivity of the calorimeter increased to a few tenths of pico-Joules per Kelvin. Therefore, it can be used to study glass transition of polymers confined in ultra-thin films down to several nanometers thickness. After the discussion of the strategy to realize fast cooling, we describe the static and dynamic thermal properties of the sensors used for the setup of the calorimeter. Finally, we present examples to show the performance of the calorimeter in different measurement modes.     

Modulated capillary titration calorimeter

A modulated capillary titration calorimeter has been developed. New software and optimization of the calorimetric unit CTD2156 are used as a basis of the modulated capillary titration calorimeter. The scanning mode of the calorimeter has been theoretically substantiated. The scanning of chambers temperature is provided due to the fact that the shield temperature is linearly varied at heating and cooling. The reversing and kinetic part of the total heat flow are measured at heating of a diluted collagen solution. The main advantage of the calorimeter is its ability to operate in a modulation mode, in an isothermal mode, in modes of linear heating and cooling of homogeneous and dispersoid liquid samples at an effective mixing of reagents in calorimetric chambers.     

卟啉化合物的热化学研究——Ⅳ.精密转动氧弹燃烧热量计的建立与标定

A precision rotating-bomb combustion calorimeter in which thermistors were used as elements of temperature control and temperature measurement was constructed in our laboratory. The calorimeter was calibrated with benzoic acid of purity 99.999 percent. The energy equivalent of standard calorimeter system is 18.6376±0.0022 kJ.K~(-1). The precision of the experiment was 0.012% (shown in the form of 2s.d m) Detailed Washburn correction was made in microcomputer with programme designed by ourselves.     

一水合邻菲罗啉的热化学性质

用纯度为99.999%的量热基准苯甲酸标定了实验室建立的精密转动弹量热计,其能当量为18604.99±8.14J/K,测得一水合邻菲罗啉(phen·H2O)的燃烧能为-5757.45±2.53kJ/mol,换算成标准燃烧焓为-5759.93±2.53kJ/mol,进而计算出一水合邻菲罗啉的标准生成焓为-391.34±2.98kJ/mol。     

A constant heat-flux calorimeter for measuring heat transfer data

A new isothermal calorimeter, designed especially for simultaneously measuring the heat of reaction and the heat transfer data in a reaction solution, is described. The system, called a Constant Heat-Flux Calorimeter, is similar to a differential scanning calorimeter in terms of direct calorimetric measurement of the energies of reaction, but differs from the conventional calorimeters described in the literature. With this device, one recorded output in a temperature control circuit is a linear function of change in energies of reaction, and second in a differential temperature control circuit is found to be proportional to a resistance to heat transfer in a solution. The performance of the calorimeter was evaluated on the basis of some results on heat transfer data of aqueous solution of polyethylene glycol and on solution polymerization of styrene at constant temperatures.     

Application of a novel type of adiabatic scanning calorimeter for high-resolution thermal data near the melting point of gallium

A novel type of adiabatic scanning calorimeter (ASC) based on Peltier elements (PEs) is used to obtain high-resolution enthalpy and heat capacity data on the melting transition of gallium. The accuracy of the specific heat capacity and specific enthalpy is about 2 %, for a sub-mK temperature resolution. The simultaneously determined equilibrium specific heat capacity and specific enthalpy are used to determine the heat of fusion and the purity. In addition, the use of the PE-based ASC as a classical heat step calorimeter and as a constant rate (DSC-type) calorimeter is discussed. A comparison of the ASC results with literature data and DSC data shows the advantages of ASC for the study of phase transitions.     

An isothermal heat flow calorimeter for large-volume applications

Design, construction, calibration, and testing of a new isothermal heat flow calorimeter suitable for investigation of large-volume specimens are presented. The measuring vessel has the volume of 1370?cm³, and the calorimeter allows for the measurement at surrounding air temperatures of 5?C60?°C. A practical application of the device is demonstrated at the determination of specific hydration heat of cement paste and concrete with silica-aggregate size of up to 16?mm, having the same water/cement ratio. The differences over the whole measuring time period of about 100?h are lower than 2% which indicates a good potential of the calorimeter for the measurement of total hydration heat of composite materials. A reference measurement of hydration heat of cement paste using common isothermal heat flow calorimeter with the measuring vessel of 1?cm³ shows an agreement within ±7%, which seems acceptable, taking into account the heat transport processes in the far larger specimens. The designed calorimeter may find use in future also in other applications where larger specimens are required, such as the measurement of adsorption heat, solution heat, various reaction heats, and enthalpy of liquid?Csolid transition in heterogeneous systems with large representative elementary volumes.     

Progress on standardization of electron beam dosimetry for radiation processing

The high dose standards and dissemination system of electron beams are being established at NIM. The graphite and/ or water calorimeters and liquid chemical dosimeter are to be accepted as standards. The transfer dosimeter selected are alanine/ESR dosimeter and radiochromic film (FWT - 60). Several kinds of radiochromic films, undyed cellulose triacetate, polyethylene and blue cellophane will be recommended as working dosimeter. A series of intercomparison studies are conducted between calorimeter and dichromate dosimeter. Agreement is found within 2%. Water calorimeters and dichromate dosimeters are used to make absolute dosimetric measurements of electron beams. These calibrated beams are then used to calibrate several types of dosimeters, such as alanine, radiochromic films, undyed and dyed polyethylene. Preliminary studies show that water calorimeter and dichromate dosimeter are reproducible and sufficiently accurate for electron beam calibration. The estimated overall uncertainty of the measurement is better than 5% at 95% confidence level.     

Design and Study of Gas Calorimeter for Absolute Measurements of the Combustion Heat of Natural Gas

A novel burning calorimeter design based on a heat pipe is presented. A circuit for automated control over operation of the proposed device is considered. The stability of the results is assessed. Several accessory parameters affecting the reproducibility of measurement results are evaluated. One of recent designs of the KTT-7 calorimeter, based on a thermosiphon, is analyzed. The uncertainty in heat power measurements on KTT-7 is evaluated.     

Which calorimeter is best? A guide for choosing the best calorimeter for a given task

Most scientists are not knowledgeable about calorimetry. The purpose of this paper is to assist the novice in calorimetry to select the best calorimeter commercially available for their task. The primary literature is a poor guide for instrument selection. Instrument developments in calorimetry are usually not reported in primary literature and calorimetric measurements are usually done with the calorimeter that is available, not the best instrument for the measurement. A procedure for choosing the best calorimeter for a given task is described.     

A direct isoperibol aneroid calorimeter

An aneroid isoperibol calorimetric apparatus is described which is particularly suitable for measurement of the reaction heat among solids. Such an apparatus contains four calorimeters and allows to carry out differential measurements. Each calorimeter includes two small electric furnaces employed for heating the solid mixture until the reaction begins and for the successive electric calibrations, respectively. The temperature trend of each calorimeter is followed by 80 thermocouples in series. The instrument characteristics are briefly discussed. Examples of its employment in the alloy thermochemistry are given.     

A new enthalpy-increment calorimeter enthalpy increments for n-hexane

A water-cooled heat-exchange calorimeter for the measurement of enthalpy increments of fluids up to 700 K and 15 MPa has been constructed. Novel features of the design ensure that heat leaks are small, well controlled, and easily measured. The results of 90 test runs on steam gave enthalpy increments in agreement with steam tables to within 0.5 per cent. The calorimeter has been used to measure enthalpy increments of n-hexane up to 573.2 K and 12.67 MPa, and the results are compared with the Starling modification of the BWR equation of state. Overall agreement of 115 measurements with the BWRS equation is 0.97 per cent. In the critical region BWRS values differ from experiment by up to 4 per cent.     

Modernization and validation of an isoperibol rotating bomb calorimeter for the measurement of energies of combustion of sulphur compounds

A rotating bomb calorimeter belonging to the Laboratory of Chemistry and Process Engineering (UCP) at ENSTA ParisTech since the 1960s was modernized and re-set in order of service for the measurement of heats of combustion of sulphur-containing compounds. The parts of the calorimeter that were replaced concerned essentially the thermal regulation, firing system and data acquisition, while most of the mechanical organs were found to work perfectly. The apparatus was tested extensively and calibrated using standard benzoic acid. The standard energy of combustion of thianthrene was measured to validate the operating protocol for sulphur compounds.     

Synergism between flame retardant and modified layered silicate on thermal stability and fire behaviour of polyurethane nanocomposite foams

Synergy in flame retardancy of polyurethane foams between phosphorus-based flame retardant (aluminium phosphinate) and layered silicates has been investigated. We used pristine montmorillonite as well as ammonium modified clay (commercially available) and diphosphonium modified clay, which were synthesised by the intercalation of the quaternary diphosphonium salt according to a procedure reported here. The morphology of the foams was characterised through X-ray diffraction (XRD), while thermal properties were characterised by oxygen index test, cone calorimeter and thermogravimetric analysis (TGA). The morphological characterisation showed that pristine and diphosphonium modified clays are almost slightly intercalated, while ammonium modified one is very well dispersed. The results of thermal characterisation showed that in the presence of phosphinate enhancements of oxygen index, fire behaviour, measured by cone calorimeter, and thermal stability have been achieved. Phosphinate is therefore an efficient flame retardant for polyurethane foams and its flame retardancy action takes place in both condensed and gas phases. Pristine and ammonium modified layered silicate bring some enhancements of thermal stability while having no important effect in decreasing peak heat release rate (PHRR) and total heat evolved (THE) when used in conjunction with phosphinate; their main advantage is related to the enhancement of compactness of the char layer formed. Diphosphonium clay is instead effective in further improving the fire behaviour of the foams because of the flame retardancy action of phosphonium: both PHRR and THE were decreased. The analysis of cone calorimeter data showed that clays act through physical effect constituting a barrier at the surface which is effective in preventing or slowing the diffusion of volatiles and oxygen, while phosphinate and phosphonium are more effective owing to their combined action in both condensed and gas phases.     

A new reaction calorimeter and calorimetric tools for safety testing at laboratory scale

Calorimetry combined with thermal analysis is an essential tool for the evaluation of thermal risks linked with chemical reactions at industrial scale. The energies of synthesis reactions or decomposition reactions as well as the heat capacities of reaction masses can be measured using such techniques. The capacity of the SETARAM differential reaction calorimeter (DRC) to determine essential safety data has been demonstrated with the measurement of heat capacities of cyclohexane and propanoic acid. Results of an industrial reaction are also presented.     

Determination of fireline intensity by oxygen consumption calorimetry

Fireline intensity is one of the most relevant quantities used in forest fire science. It helps to evaluate the effects of fuel treatment on fire behavior, to establish limits for prescribed burning. It is also used as a quantitative basis to support fire suppression activities. However, its measurement is particularly tricky for different reasons: difficulty in measuring the weight of the fuel consumed in the active fire front, difficulty to evaluate the rate of spread of the fire front, and uncertainty on combustion efficiency. In this study, an innovative and original approach to directly measure the fireline intensity at laboratory scale is proposed. Based on the oxygen consumption calorimetry principle, this methodology is applied here in case of spreading fires, for the first time. It allows for directly measuring the heat released by the fire front. The results are then used to test the famous Byram’s formulation that is generally applied to determine the fireline intensity. Combustion efficiency and effective heat of combustion results are provided. The uncertainty and the use of a full scale calorimeter instead of a bench scale calorimeter for this study are discussed.     

Heat Capacity Measurements Using Temperature-modulated Heat Flux DSC with Close Control of the Heater Temperature

The determination of heat capacity data with sawtooth-type, temperature-modulated differential scanning calorimetry is analyzed using the Mettler-Toledo 820 ADSC™temperature-modulated differential scanning calorimeter (TMDSC). Heat capacities were calculated via the amplitudes of the first and higher harmonics of the Fourier series of the heat flow and heating rates. At modulation periods lower than about 150 s, the heat capacity deviates increasingly to smaller values and requires a calibration as function of frequency. An earlier derived correction function which was applied to the sample temperature-controlled power compensation calorimeter enables an empirical correction down to modulation periods of about 20 s. The correction function is determined by analysis of the higher harmonics of the Fourier transform from a single measurement of sufficient long modulation period. The correction function reveals that the time constant of the instrument is about 5 s rad⁻¹ when a standard aluminum pan is used. The influence of pan type and sample mass on the time constant is determined, the correction for the asymmetry of the system is described, and the effect of smoothing of the modulated heat flow rate data is discussed. This revised version was published online in July 2006 with corrections to the Cover Date.     

Development of polystyrene calorimeter for application at electron energies down to 1.5 MeV

Polystyrene (PS) calorimeters developed at Riso National Laboratory for use below 4 MeV have been modified due to irradiation technology requirements concerning both design principles and dimensions. The temperature–time relationship after irradiation was measured, and two ways of dose measurement were tested: (1) real time temperature measurement during the irradiation and (2) pre- and post-irradiation temperature measurement. The advantages and drawbacks of these methods are discussed.Depth dose measurements have been carried out in the PS calorimeter to define the relationship between the average and the surface dose and to prove the applicability of the new low energy calorimeter for calibration purposes at 1.5 and 2 MeV electron energy. Alanine dosimeters of 2 mm thickness were used to calibrate the calorimeters and their use for nominal dose measurements was demonstrated in a series of intercomparisons. The use as routine dosimeters at electron accelerators operating in the energy range of 1.5–4 MeV was also demonstrated.     

New Isothermal Titration Calorimeter for Investigations on Very Small Samples. Theoretical and experimental studies

A new isothermal titration calorimeter with 78.5 μL volume capillary chambers has been developed. It is based on the theory of mixing reagents in a capillary chamber of a titration calorimeter and separation of the sensitive volume of chambers in a differential calorimeter. The evaluation of the efficiency of diffusion mixing is described by means of an oscillating dispensing needle. The calorimeter was tested by the reactions: Ba²⁺– 18-Crown-6 and Rnase-2’CMP. The main advantages of the new titration calorimeter are the use of very small amounts of reagents, the high accuracy of separating the sensitive volume of calorimetric chambers and the minimization of power input while mixing reagents in a horizontally located capillary chamber. This revised version was published online in August 2006 with corrections to the Cover Date.