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Metrological prospects for the assessment of transition plateaus

This article has been downloaded from IOPscience. Please scroll down to see the full text article. 2010 Metrologia 47 349 (http://iopscience.iop.org/0026-1394/47/4/001) View the table of contents for this issue, or go to the journal homepage for more

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IOP PUBLISHING Metrologia 47 (2010) 349356

METROLOGIA doi:10.1088/0026-1394/47/4/001

Metrological prospects for the assessment of transition plateaus

E Gaviot1 , G Failleau1,2 , R Morice2 , L Camberlein1 , F Polet1 and B B eche3,4
1 Laboratoire dAcoustique de lUniversit e du Maine, Micro Cap Ouest, LAUM, UMR CNRS 6613, Le Mans, France 2 Laboratoire Commun de M etrologie (LNE-Cnam), Paris, France 3 Institut de Physique de Rennes, IPR, UMR CNRS 6251, Rennes, France 4 Institut Universitaire de France (IUF), 103 bd Saint-Michel, 75005 Paris, France

Received 10 December 2009, in nal form 6 April 2010 Published 20 May 2010 Online at stacks.iop.org/Met/47/349 Abstract Heat ow transducers have been implemented within a thermometric xed-point cell operated with indium. Then a local heat ow rate was monitored simultaneously with the classical temperature measurement. A specic conguration, so-called cell-within-cell, allowed us to control a melting transition plateau and to observe the behaviour of the heat exchanged during the whole process of the melting transition. Owing to their dynamic character, heat ow measurements prove to be the most appropriate for dening specic boundaries on a given transition plateau, and relevant sensors are found to be suitable tools to be coupled with enhanced temperature measurements. This piece of work is presented in two parts, with the description of the set-up and measurement results in this rst paper and their subsequent thermodynamic implications in the following one.

1. Introduction
1.1. Description of classical prerequisite and approach for consistent results The freezing point of indium at one standard atmosphere (at 156.5985 C) is one of the xed points specied for use in the denition of the International Temperature Scale of 1990 (ITS-90) [1]. As regards precise calibration for any xed point above room temperature, many factors including the materials of the cell component and minimization of its internal temperature gradients may affect the quality of the whole process. High purity metals, pure graphite crucibles and inert gas such as argon lling the cell are basic requirements to avoid any form of chemical contamination. As such prerequisites are met, a relevant thermal measurement policy has to be dened accounting for any form of extraneous temperature gradients through the cell, the ideal condition being that of perfect temperature stability. To this end, classical designs of the state of the art have been improved considering the so-called cell-within-cell devices recently developed with the LNE for adiabatic calorimetry [2, 3]. As a second major requirement, low-noise temperature sensors
0026-1394/10/040349+08$30.00

tted with rst-rate conditioners are especially suited. Most commonly, as the measuring process is started, a platinum resistance thermometer (PRT 25 ) together with a highquality resistance bridge, such as ASL F900 (measurement resolution; 50 K), allow best performance. 1.2. Issues arising from the interpretation of recorded data Reliable thermal investigations hinge on the thermodynamic stability of both phases, according to a mandatory long-lasting melting or freezing process. The best quality of any given phase transition should be considered as when the liquid/solid interface is be shaped as a front-wall parallel to the axis of the cell, propagating as slowly as possible. Despite allowing such a thermal condition, classical designs only rely on temperature sensors to monitor the stability of the process together with its dynamic properties; however, both specications are quite paradoxical, with oxymoronic expectations considering both accuracy and response time. The whole process must be investigated after having recorded and plotted the temperature measurement values, with its specic points between both ends of the plateau dened so as to consider an effective domain of best temperature uniformity in the cell.
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E Gaviot et al

(a)

(b)

Figure 1. (a) View of the global set-up. (b) Fitting the cell into the furnace.

Theoretically, both stability and dynamic evolution could be dealt with if precise energy monitoring could be ensured. Although practically never considered, the concept is most valuable in assessing both temperature uniformity and dynamic evolution of the system. In this paper, we take advantage of coupling the classical temperature monitoring together with a high-quality local heat ow measurement. Thanks to such an approach, in the subsequent paper, a straightforward thermodynamic rationale will be presented to get a better understanding of the phase transitions observed on the shape of a classical plateau.

2. Set-up, sensors and measurements

2.1. Measurement specications, set-up and cell-within-cell design Melting processes have been performed considering the following grounds and motivation: as a complementary investigation with the freezing transition specied in ITS-90, this study was aimed at specic melting processes performed by way of adiabatic calorimetry. As the conguration of the cell and its guard were designed with a view to screening out any untoward heat exchange, we conjectured that under stringent heat ow monitoring, a melting process could be carefully achieved with valuable results from a proper treatment of concomitant measurements of both temperature and heat ow. Since our main goal was to control the energy balance precisely, we had to avoid the thermal disturbance usually associated with breaking the supercooling mechanisms characterizing the freezing transition. The global set-up of the experiment is shown in gure 1(a). Then, melting process investigations were carried out considering the following specications: the temperature within the cell was monitored by way of a PRT-25 , with a state of the art ASL F900 resistance bridge as shown in gure 1(a). This type of bridge allows temperature 350

measurements with a resolution of 50 K [4]. The purity of the indium load was 99.9999% (6N) as required by ITS-90 standards [5]. As depicted in gure 1(b), the cell was arranged within a home-made furnace (LNE) whose temperature was kept about 0.5 C below the phase transition, prior to beginning both cell control and data recording. As tuning such an apparatus (furnace, guards, inner cell) is a rather lengthy process due to the different heat capacities of the materials involved, the whole melting experiments required durations up to 12 h. As xed-point cells are highly sensitive metrological devices, a specic guarded cell, the so-called cell-within-cell, was designed [2, 3], as illustrated on a reduced scale crosssection in the left of gure 2(a). The main point of such an elaborate design hinges on the following rationale: as such, the cell-within-cell is based on a classical cell inserted into an isothermal structure whose isothermal condition is ensured with the same material (in its changing state) as that experimented with. Considering as veried the classical and mandatory metrological measurement provisions, such a cell should allow better performance than if the same unit were to be directly arranged within a standard controlled furnace. As a main characteristic, the mass of indium in use within the outer guard is substantially greater than that within the inner cell, whose transition time is then shorter than that of the guard. The masses of indium involved in the whole cell were, respectively, 850 g in the outer guard, 123.39 g in the upper inner guard and 115.96 g for the material under experiment. Photographs of the outer guard together with the inner cell are illustrated in the right side of gure 2(b). Practically, to operate such a device, auxiliary heaters were used, their energy dissipated being measured throughout the process, to ensure the required long-melting phase transition in the inner cell. As regards a mandatory validation of the design, temperature measurements have been carried out while shifting upwards the PRT-25 device within the frosted Pyrex well. Then the measured values may be compared with the theoretical ones taking account of the corrections due to
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Metrological prospects for the assessment of transition plateaus

Figure 2. (a) Cell-within-cell cross-section. (b) Main pieces of the cell assembly.

Figure 3. Survey of the temperature eld within the cell-within-cell device, taking account of the corrections due to hydrostatic pressure changes.

hydrostatic pressure changes associated with the levels within the indium. As a result, such a validating process may be illustrated as depicted in gure 3. Despite raising the sensor by translation up to 80 mm within the well, the consequential reduced deviation of the measured values from the theoretical dashed line provides strong evidence of the merits of the cellwithin-cell design. 2.2. Specications of heat ow meters (HFMs) HFMs have long been classical devices, commercialized for various industrial purposes generally operating under 250 C. The heat owing through their sensing surface generates an emf strictly proportional to its magnitude: then, combined with a temperature sensor, a local exchanged entropy current can be measured. As self-generating sensors, HFMs rely on
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thin planar thermopiles that may be optimized in terms of materials, geometry and implementation as described in the literature [6, 7]. Specic devices developed in the laboratory supply low-noise signals (Z 25 k ) that can be monitored with a low-drift chopper-stabilized amplier (TLC 2652, gain = 50, residual offset measured and compensated for by way of software), according to their signicant sensitivity averaging 10 V W1 m2 . Based on machinable ceramics and microtechnologies, specic prototypes (MCO) have proved to withstand temperatures up to 700 C with a view to investigating aluminium phase transitions. As regards the considered metrological application, the temperature being quasi-invariant over the plateau, any prospective temperature drift of the sensor can be neglected. Moreover, both chromel and alumel alloys involved in the thermopile are classical materials often dealt with in thermal engineering. 351

E Gaviot et al

Figure 4. Simultaneous measurements of temperature and heat ow rate against time.

As zeroing devices, HFMs are found to be a fortunate solution to prove the relevance of the cell-within-cell conguration, insofar as both sensitivity and low Johnson noise allow accurate information about heat losses. Then, with VNoise-RMS = 20 nV Hz1/2 and the operative frequency bandwidth being limited to 100 Hz, an ideal resolution close to MCO 20 mW m2 may be expected. Practically, experimental assessments involving both a shunt and a thin-lm metallic 25 k resistor linked to the whole data processing channel were mandatory to be compared with in situ measurements. 2.3. Implementation of heat ow transducers First experiments, operated with standard commercial units, allowed us to take advantage of the at bottom of the inner cell to implement the main HFM, with a thin Teon layer ensuring thermal contact. To this end the ceramic substrate was polished on both faces, besides allowing classical microtechnology processes. A schematic view of the cell studied is depicted in gure 2(a). The mass of the indium in the inner cell, Min = (115.96 0.02) g, and its melting enthalpy is Hmelt = (3313.7 8.7) J (with L = (28 576 70) J kg1 ). Although the sensing surface ( = 2.5 2.5 cm2 ) is quite incomplete as regards the effective system boundary [8], the real-time local evolution can be monitored, and an apparatus constant , being conceptually representative of an ideal surface, may be dened to account for the effective frontier, provided the environment is devoid of major temperature gradients. Such a criterion is practically met as the plateau is observed in the cell-within-cell conguration. Then, the sensor was arranged so as to supply a negative voltage if heat owed from the bottom of the cell down to its encompassing guard. Such a signal accounts for the heat balance stemming from conduction, convection and radiation mechanisms, insofar as the guard is veried to remain in its own transition state. Furthermore two auxiliary standard units were implemented for cross-correlation of their relevant data. It must be highlighted that as such sensors were implemented, their thermal internal resistance could yield a slight shift in the 352

plateau temperature, averaging up to 15 K as can be estimated by way of modelling [9].

3. Results and treatment

3.1. Straightforward observations As a typical example of recording, the local heat ow rate density m together with temperature values are plotted in gure 4. The classical temperature pattern can be signicantly highlighted by that of the exchanged heat ow despite a relatively small sensing area. The local heat ow pattern shows three major regimes, respectively associated with solid heating (R1), transition (latent heat exchanged, R2) and liquid heating (R3). It must be underlined that during the whole experiment, the outer guard is ensured to remain in its own transition state. As regards information, the discontinuities, sign, magnitude and extraneous uctuations of the signal can be interpreted as follows: at rst, compared with the temperature recording, the so-called solidus point can be localized more rapidly and more easily by way of the zero-crossing associated with the rst discontinuities. Similar considerations will be dealt with later with regard to both melt-off (liquidus) and runoff points, usually dened by way of drawing tangent lines on the temperature recording. Considering the sign, negative values associated with R1 highlight the incoming ow from the guard (whose temperature is driven by its own transition state) into the inner cell with the whole load of indium still in the solid state. Moreover, the heat ow supplied from the auxiliary heater is superimposed in such a way that the second regime R2 shows a self-stabilization of the cell characterized with both liquid and solid. Then the whole heat ow rate supplied by the auxiliary heater is a priori distributed as shown in gure 5, in such a way that only a tiny quantity, with a density of heat ow averaging m 300 mW m2 , proceeds through the sensor (due to the graphite material IG-210; = 116 W (m K)1 ) down to the outer guard. As regards the third regime R3, beyond the so-called meltoff point [10], the whole content of the inner cell is in the liquid state: then, the noticeably increasing positive local heat ow
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Metrological prospects for the assessment of transition plateaus

Figure 5. Photograph of heat ux sensors implemented in a cell-within-cell adiabatic calorimeter and elements for modelling heat exchanges. Table 1. Selected samples for detecting the boundaries of the plateau. Relevant samples (20.113 s), time/h N 128 (solidus): 0.683 36 N 129 (solidus): 0.688 92 N 1288 (melting): 7.172 26 N 1374 (liquidus): 7.650 03 N 1375 (liquidus): 7.655 59 N 1376 (liquidus): 7.661 15 MCO Heat ow rate/W m 2 0.075 67 (before zero-crossing) +0.142 86 (after zero-crossing) +0.376 80 +0.455 09 +0.455 10 +0.463 58 Temperature (PT25)/ C tsol = 156.5645 tsol = 156.5659 tmelt = 156.5988 tliq = 156.6317 tliq = 156.6330 tliq = 156.6342

rate values highlight the overheating of the inner cell (indium in liquid state) into the encompassing guard still in its transition state. 3.2. Heat ow uctuations highlighting the boundaries of the plateau Heat ow uctuations can be observed from the beginning of the plateau, where they can be interpreted as associated with the initiation and organization of the thin supercial liquid lm. However, as depicted in gure 4 the partially chaotic character of the process is not easily made clear since the noise related to the whole measurement channel and the considered uctuations are of the same order of magnitude. Moreover, if such local variations were identied from the noise, they would stem from inner extraneous heat transfers marking the presence of both phases: then the span of the whole plateau could be dened as long as the uctuations can be observed: as a matter of fact, proceeding in such a way allows a time accuracy to be achieved which is close to that of two sampling periods (2 20 s (plateau-duration) 25 080 s or 6.966 h).
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We have to stress what would happen if the auxiliary heater were to be switched off during R2; then, separate experiments were found to bring the locally measured heat ow to a centred signal with the same terms and magnitude as that of the above mentioned uctuations. The separate box depicted in gure 4 illustrates the comparison between a one hour sequence of recorded heat ow rate density and the noise stemming from a thin-lm metallic 25 k resistor at room temperature adjusted to the average level of the set of points. Then signal processing is essential to investigate the level, shape and nature of the uctuations. However, such a uctuation mechanism provides a source of information about the melting process since both solidus and liquidus boundaries of the plateau can be clearly identied as 156.5645 C < tsol < 156.5659 C and 156.6317 C < tliq < 156.6330 C: the latter values provide strong evidence that a 20 s sampling time is not short enough to achieve optimal results. Relevant samples are summarized in table 1. Apart from such observations, a classical determination of the melting temperature by way of tangent lines yields tmelt = 156.5988 C. As regards design it is clear that the best conguration of any cell should lead to the minimization of 353

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Figure 6. Equivalent networks for modelling sensible heat transfer and latent heat transfer.

any kind of thermal uctuation since their magnitude and frequency are essentially associated with entropy generation altering any process [11]. As such, the cell-within-cell conguration stands as a most interesting design. 3.3. How to illustrate the global heat ow behaviour So as to understand the energy balance during the process, a simple electrical network analogy can be identied in order to highlight the meaning of the output voltage stemming from the main HFM. Then the net ow through its sensing area is m = m . 3.3.1. Steady state for each regime. Both regimes R1 and R3 can be analysed in terms of sensible heat transfer mechanisms that can be accounted for by both top networks depicted in gure 6. As long as the indium is in the solid state (R1) the guard supplies a given heat ow rate into the inner cell in such a way that m < 0. Considering R3, m is clearly positive as the temperature is higher in the liquid inner cell than in the guard that is still in the transition state, and the auxiliary heater supplies a global heat ow rate into the outer guard ( go ) and through the graphite wall of the inner cell ( in ; Rgi ). This component ( go ) is partly detected with the HFM, with m in . The regime (R2) to be investigated can be analysed in terms of latent heat as the behaviour of the load of indium is close to that of a perfect voltage source with internal resistance close to zero (shunt). In this way, as both the guard and the indium can be seen as such perfect sources according to Thevenin, the heat ow sensor acts in series with the resistor associated with the gap (air 4 mm) between the sensor and the bottom wall of the outer guard. Such electrical considerations are often encountered in the classical approach to systems analysis [12]. 354

In most electrical network analogies, any HFM may be compared with an ammeter thanks to its low thermal resistance. Conversely, with the transition regime R2, such a sensor arranged in series with acts as a non-invasive voltmeter, especially tted to investigate the in component accounting for the amount of heat ow supplied for performing the state transition (insofar as the shunt ShXY remains zeroed). Considering the whole plateau, the energy supplied by the auxiliary resistor was measured as Wh = (5166 10) J, while the latent heat provided to the indium was Hmelt = (3313 8.6) J. Then, the effective part conveyed into the indium was close to 64%. 3.3.2. Running out of the plateau. To underline the limits of such simple models, one must distinguish between the two transitions (R1 R2) and (R2 R3). The rst one, which is marked with the zero-crossing, is quite instantaneous, but the second one is clearly a more complex process. As shown in gure 4, the heat ow rate density before the end of the plateau (R2 R3) highlights the so-called run-off point (sample 1105; trun-off = 156.5957 C) inferred from the steady rise in local heat ow rate. Beyond the run-off point, the shift from the latent heat transfer mechanism to the linear sensible heat mechanism (R3) is not instantaneous and is marked with moving solid clusters in the cell, while the liquid phase (in a much higher fraction in the cell) is half as thermally conducting as the remaining solid material (liq = 42 W (m K)1 , sol = 81.8 W (m K)1 ). As depicted in gure 6, before the (R2 R3) shift, the sensor directly highlights the ow incoming into Rgo . Then, as shown in gure 4, the increase in local heat ow observed with time (ro < < mo ) is representative of a relative decay of in since the heater provides a constant power h = in + go . Close to the melt-off point, we assume the observed behaviour is that of an elementary evolving network, as if the leg
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Metrological prospects for the assessment of transition plateaus

Figure 7. Balance of distributed energy over the melting plateau.

5.5 mW (m K)1 ) rather than air were used, increasing then Rgo and gap , and enhancing the adiabatic property of the cell and the non-invasive character of the heat ow rate measurement. Obviously, the energy balance monitoring should be more accurately performed with more sensors judiciously arranged around the inner cell. Such a measurement policy together with the ability to perform in situ calibration should allow signicant amounts of freedom as regards the sensor or the geometry and size of the cell. The later considerations suggest the possibility to miniaturize specic cells for industrial purposes. Moreover, as will be shown in the following paper, the energy balance monitoring may bring about further valuable information (to our knowledge never reported until now) on a given xedpoint cell.

containing SXY were a shifting channel, the link ZZ switching to X Z . Such a change as a process should neither generate nor consume energy. As the HFM displays the part owing into the outer guard, an apparatus constant can be dened considering the whole plateau with [W h
mo Hmelt ] 0 =

5. Conclusions
The design of the so-called cell-within-cell conguration allows high-quality temperature measurement during the melting of indium. Simultaneous measurements of temperature and heat ow allow accurate monitoring and investigation of a phase transition within a thermometric xed-point cell. Although a faster sampling should be performed so as to enhance our approach, the key points of the plateau are easily identied and are in agreement with the classical methods based on tangent line drawings. Heat ow measurements prove that the cell-within-cell conguration is highly effective as regards the expected adiabatic condition. These experiments involving a high-quality HMF clearly show that the energy balance can be illustrated during the whole transition process. Then, as specic HFMs can be judiciously implemented, it is expected that heat ow measurements within optimized metrological xed-point cells will soon be considered as a most advantageous approach to enhancing the quality of measurement.

mo go (t) 0

dt =

mo 0

m (t) dt (1)

(with in m2 ).

Consequently, the constant is established as = (0.235 75 0.0076) m2 and in ( ) = h m ( ). Then, the global pattern describing the latent heat supplied within the indium can be deduced from equation (1) together with the sensible heat owing into the guard. Considering such exchanges counted from 0 until mo the energy balance evolution is illustrated in gure 7. The plot Qin ( ) highlights, beyond the run-off, the decreasing slope of the stored energy (Qin ( ) being the net ow in ( ) integrated over time as 0 < < mo ). Finally, as the plateau can be dened with both temperature as a function of time T ( ) and the supplied quantity Qin ( ), a parametric description may be considered in terms of t C = f (Qin ) so as to screen out any time representation. This point will be investigated in the second part of this work. Hence, as regards investigation on the regime R2 about the balance of energy inferred from the main HFM signals, the way to proceed on our rationale with equation (1) is tantamount to in situ calibration.

Acknowledgments
The authors would like to thank Professor P Thery and F Raucoules with Captec (SARL) for their fruitful discussions about comparison between standard commercialized sensors and the prototypes developed in our laboratory. They are grateful to P Ridoux (LNE) for his most helpful management especially regarding the development of the cell-within-cell conguration. G Failleau would like to thank N Fleurence for contributing valuable experiments that helped improve the quality of this paper.

4. Prospects
These rst experiments involving HFMs clearly show the interest in coupling such devices with temperature sensors for monitoring both steady and unsteady states. The most signicant enhancement to consider concerns both sensitivity and low noise, together with the ability to withstand high temperature environments. Moreover, a faster sampling should improve the reading of the key points. The results demonstrate that the auxiliary heater could be advantageously controlled by way of an appropriate HMF, so as to obtain especially long durations if required for studying any state transition. On the other hand gure 6 suggests an optimization of the whole conguration if an insulating gas such as xenon ( =
Metrologia, 47 (2010) 349356

References
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