Blackwell Science, LtdOxford, UKJFPEJournal of Food Process Engineering0145-8876Copyright 2004 by Food & Nutrition Press, Inc., Trumbull, Connecticut.

2004275359376Original Article HIGH-PRESSURE DSC: EQUIPMENT/TECHNIQUE VALIDATION ET AL. S. ZHU

HIGH-PRESSURE DIFFERENTIAL SCANNING CALORIMETRY (DSC): EQUIPMENT AND TECHNIQUE VALIDATION USING WATERICE PHASE-TRANSITION DATA
S. ZHU1, S. BULUT2, A. LE BAIL2 and H.S. RAMASWAMY1,3
1

Department of Food Science and Agricultural Chemistry McGill University 21111 Lakeshore Road, Ste Anne de Bellevue, Quebec H9X 3V9Canada 2 GEPA-ENITIAA (UMR CNRS 6144-SPI) Rue de la Graudire BP 82225, F-44322 Nantes Cedex 03, France
Accepted for Publication June 18, 2004

ABSTRACT Understanding phase transition during high-pressure (HP) processing of foods is important both with respect to optimizing the process and improvement of product quality, but scientic information available in this area is very limited. In this study, the phase-transition behavior of water was evaluated using a HP differential scanning calorimetry (DSC). Tests were carried out under both isothermal pressure-scan (P-scan) and isobaric temperature-scan (T-scan) modes with distilled water prefrozen in the sample cell. P-scan was carried out at 0.3 MPa/min at two temperatures, -10 and -20C, and T-scan was carried out at 0.15C/min at two pressures, 0.1 and 115 MPa. The pressure-induced phase transition of water was accurately reproduced by the P-scan test. Ice melting latent heat during P-scan showed no signicant difference (P > 0.05) from the available reference data in literature. The relationship between P-scan tested (Lm) and reference latent heat was Lm = 0.987 L (R2 = 0.99, n = 6) suggesting a mean error less than 2%. T-scan mode was less appropriate and did not yield promising result. Measured values were less accurate than P-scan probably because of the inuence of large heat capacity of sample cell. However, reliable and reproducible results obtained under P-scan mode suggested that the HP DSC can be used for the calorimetric determination of pressure-dependent water-phase transition in real food systems during HP freezing/thawing operations.
3

Corresponding author. TEL: Hosahalli.Ramaswamy@McGill.ca

+1-514-398-7919;

FAX:

+1-514-398-7977;

EMAIL:

Journal of Food Process Engineering 27 (2004) 359376. All Rights Reserved. Copyright 2004, Blackwell Publishing

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INTRODUCTION High-pressure (HP) process is receiving considerable attention because of its advantages and potential benets for the preservation and modication of foods. Phase transition is one of the major domains that are of potential interest in HP processing of foods. Pressure-induced phase transitions, such as freezing/thawing of high-moisture foods and crystallization of lipids, offer numerous opportunities for process or product development (Knorr 1999). Water undergoes different types of phase transitions when subjected to different pressuretemperature domains (Bridgman 1912). This phenomenon allows carrying out different freezing/thawing applications such as pressure shift freezing, HP freezing and HP thawing (Cheftel et al. 2000). HP in this context generally refers to pressures in excess of several hundred atmospheres (>50 MPa). Calorimetry is a powerful tool to study thermodynamic properties of materials and phase-change phenomena. Normally, calorimetric experiments are carried out with a differential scanning calorimeter (DSC) at a constant (usually atmospheric) pressure using temperature as the working parameter. Bridgman (1912) developed experimental apparatus to measure phase transition and volume change of pure water under pressure, and to estimate latent heat of water using Clapeyron equation. Hogenboom et al. (1995) developed a similar apparatus with a novel piezometer to measure volume variation and phase diagram of an aqueous magnesium sulfate solution. In HP calorimetry, the cell for holding the sample should be strong enough to resist high pressure. Thus, the cell becomes large in terms of mass and heat capacity, which presents a major challenge to obtain accurate results for temperature scan (T-scan) tests. To overcome this difculty, an alternative measure of pressure scan (P-scan) at a constant temperature is adopted in HP calorimetry. The pressure can be changed either as a step change (Pruzan et al. 1979) or at a constant rate (Randzio et al. 1994). Several studies have been carried out using P-scan tests for gathering thermal properties of water and aqueous solution (Chourot et al. 2000; Le Bail et al. 2001) and some organic liquids such as hexane, butane-1, benzene, toluene (Fuchs et al. 1979; Pruzan et al. 1979; TerMinassian et al. 1988; Grolier and Randzio 1997) under HP conditions. Two types of calorimetric apparatus have been used in terms of working conditions: constant mass or constant volume. Most of the studies in literature are related to liquids and used constant volume technique (Pruzan et al. 1979; Randzio et al. 1994; Le Bail et al. 2001). Most foods and food products contain a high percentage of moisture. Thermo-physical properties of foods have been generally linked to moisture content, temperature, phase and pressure. Phase transition of water in these foods during HP process can be more complicated than that of pure water.

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Scientic information related to HP calorimetry of foods is scarce and poorly documented. The objective of this study was to evaluate the performance of HP DSC for characterizing the phase-transition behavior of water at high pressures by employing two modes: (1) the traditional T-Scan and (2) the more recommended P-scan. A specic objective was to validate the technique by comparing the experimental results on phase-transition temperatures and latent heat of pure water with published data and thereby pave way for the use of the technique for gathering data on HP water-phase transition in foods.

MATERIALS AND METHODS HP Calorimetric System A HP DSC (Fig. 1) was used in this study. The experimental system consisted of a differential calorimetry head, a refrigerated circulator, two HP cells, a HP compressor and a computer. The calorimetry head (Pass 27, Sceres, Orsay, France) had two cavities (20 mm diameter 95 mm depth) used for holding the sample and the reference cells. There were 220 thermocouple junctions installed between the two cavities to amplify the generated temperature differential signal. Two platinum thermometers (Pt 100) were placed under each of the cavities to monitor/control temperature of the calorimeter. The temperature of the calorimetry head was controlled through a copper coil winding around the contour of the head (Fig. 1a) and an oven around the system. The copper coil was connected to the refrigerated circulator (Huber CC250, Offenburg, Germany) with a water-glycol medium. During the experiment, the calorimetric head together with copper coil was thermally insulated in plastic box containing foamed plastics. The HP cell (made of beryllium copper) contained two plugs with nitrile O-ring and a threaded bolt for sealing on one side (Fig. 2). It was connected to a pressure tube (3.2 mm diameter) on the other side with miniature ttings (M2 Serie, 100 MPa, Harwood Engineering, MA). The pressure within the system was achieved through the HP compressor (400 MPa, 5 cm3, NovaSwiss, Effretikon, CH) driven by a step motor (MO63-LE09, Mijno, Fenwick, France) and controlled by the computer. A pressure sensor (200 or 400 MPa, Asco Instruments, Chateaufort, France) was used to monitor and control the pressure. When the pressure required for a test exceeded 180 MPa, the 400MPa sensor was used during the experiment. A software (Labview 6, National instruments, Austin, TX) was used for system control and data recording (temperature, pressure and heat ow). Pentane (Sigma, Fallavier, France) was used as pressurization medium in the system because of its stability on the

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(a)

Calorimetric head

HP compressor Medium reservoir Cell HP sensor

Refrigerated circulator

Copper coil

Computer
(b) HP cell Calorimetric head

HP tube

Copper coil

FIG. 1. EXPERIMENTAL SET-UP OF HP DIFFERENTIAL SCANNING CALORIMETER: (a) schematic diagram and (b) photograph of the calorimetric head and the cells.

pressuretemperature domain tested and its properties (low viscosity, no phase change) (Bridgman 1970; Scaife and Lyons 1980). Calibration The pressure sensor was calibrated against a reference pressure gauge (Bourdon, France). Temperature of the calorimeter was calibrated against a

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FIG. 2. SCHEME OF THE HIGH-PRESSURE CELL AND SAMPLE INSTALLATION

K-type thermocouple (0.1 mm diameter, Omega, Stamford, CT) placed in the sample cell at selected temperature between -20 and 20C. The calorimeter was calibrated using a 100 W resistance settled in the sample cell. A voltage between 1 and 4.2 V was supplied to this resistance by a power source (220 programmable voltage source, Keithley Instruments SARL, Saint-Aubin, France) for period between 30 and 90 min. The heat generated from the resistance was evaluated with the voltage and the current measured with a voltmeter (7055 Voltmeter, Solartron Mobrey SA, Saint-Christophe, France) and an ampere meter (195A multimeter, Keithley Instruments, SARL, SaintAubin, France). The calorimetry differential temperature signal (mV) attributed to the electric heating was recorded every 5 s. The peak area was then integrated to calculate the ratio of heat power to calorimetric voltage at selected temperatures. The calibration tests were carried out from -20 to 20C. A linear t of the experimental data was obtained as:
q = kS = (37.1 + 0.080T )S

( R2 = 0.978, n = 8),

(1)

where q is heat ow rate (mW); S is calorimetric signal (mV); k is the ratio of heat ow rate to calorimetric signal (mW/mV); T is the temperature of the calibration tests performed (C). Similar calibration procedures have been used in the study by Chourot et al. (2000) and by Le Bail et al. (2001). Sample Preparation All experiments were carried out using distilled water. About 0.5 g of pure water (weight accurately measured up to milligram level; example 0.5712 g) was vacuum-packaged in a polyethylene bag (80-mm-thick multiplayer lm) (La Bovida, Nice, France). For the test, the sample was installed

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in the sample cell (see Figs. 1 and 2). The reference cell was prepared in the same way as the sample cell but without the sample. Air bubble was carefully removed from the cell during the preparation of the two-calorimeter cells. Isothermal Pressure-Scan (P-Scan) After sample installation, the sample and reference cells were placed in the sample and reference cavities, respectively. The sample was frozen at the set temperature (-10 or -20C) in the calorimeter. Once the calorimeter signal showed a stable baseline (close to zero), the pressure was increased from the atmospheric level (0.1 MPa) at a constant rate (0.3 MPa/min) up to a level high enough for completion of the melting process (e.g., 160 MPa for the Pscan at -10C) and heat ow signal was recorded every 5 s (Fig. 3). When the pressure reached the corresponding phase-change temperature, ice started melting (see point 1 in Fig. 3), resulting in a peak of heat ow to compensate for the temperature drop. A low P-scan rate was employed in this study, as compared to 1 MPa/min in some previous studies (Le Bail et al. 2001), in order to obtain a well dened span of calorimetric peak. Isobaric Temperature-Scan (T-Scan) T-scan tests were carried out at constant pressure (Fig. 4) by increasing the temperature at a prescribed rate. Before each T-scan test, the test sample was frozen in the calorimeter and then stabilized at 0.1 MPa or 115 MPa, corresponding to a phase-change temperature of about 0 or -10C, respectively (Bridgman 1912). When calorimetric signals approached a balance under a constant pressure, the temperature was increased from lower than -15C at a constant rate (about 0.15C/min) and the calorimeter signals were recorded every 5 s.

RESULTS AND DISCUSSION Isothermal P-scan Figure 5 shows a typical experimental differential thermograph of an isothermal P-scan with pure ice at the calorimetric temperature of -10C. By calibration using Eq. (1), calorimetric data is converted into heat ow rate. Figure 6a demonstrates two peaks of heat ow rate against pressure during Pscan of the ice samples at calorimetric temperature -10 and -20C, respectively. The HP DSC heat ow signal appeared a straight baseline as pressure was increased at a constant rate. As the pressure level increased, the signal started deviating from the base line (1 in Figs. 3 and 5). This transition was

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(a) 0 Temperature (C) Water

TC

P-scan

Ice-I 21 0.1 P1

P2

P3

210

Pressure (MPa) (b) 0.1 Calorimetric signal (endo down) 0 1 Peak onset (melting start) 3 Peak baseline Peak end Pressure (MPa) P1 P2 P3

Peak 2 (melting end)

FIG. 3. SCHEMATIC DESCRIPTION OF ISOTHERMAL PRESSURE-SCAN: (a) water phase-change diagram and pressurization and (b) corresponding calorimetric signal (Tc is calorimetric temperture [C]).

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0 Temperature (C)

T-scan

Water

Ice-I 21 0.1 Pressure (MPa) 210

FIG. 4. SCHEMATIC DESCRIPTION OF ISOBARIC TEMPERATURE-SCAN WITH WATER PHASE-CHANGE DIAGRAM

0.3
Heat flow signal (mV)

160 140 Heat flow signal

1 3

0.0 0.3 0.6 0.9 1.2 1.5 1.8 0 60 120 180

t1

100 80 Pressure
2

60 40 20 240
t2

300

t3

360

Time (min)
FIG. 5. A TYPICAL MEASUREMENT OF ISOTHERMAL PRESSURE-SCAN (0.3 MPa/min) OF PURE ICE (0.5712 g) WITH CALORIMETRIC TEMPERATURE AT -10C

Pressure (MPa)

120

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dened as onset temperature in this study. In the case of P-scan test, this onset refers to the pressure that is associated with the beginning of the melting of test sample (ice). For P-scan at -10 and -20C, the onset pressure was 111 1.8 (mean SD, n = 3) and 194 1.5 MPa (n = 3) (Fig. 6a), respectively, which matched well with phase-change diagram of waterice I (Bridgman 1912), as empirically expressed by Bridgman (1912) as follows:
TP = -0.0722 P - 0.000155P 2

(2)

where TP is phase-change temperature of water (C); P is pressure (MPa) (Chourot et al. 1997). After onset, the temperature of the ice/water mixture decreases with a further increase in pressure (12 in Fig. 3a), following pressuretemperature relationship of the phase change of waterice I (Bridgman 1912; Le Bail et al. 2002). This phenomenon enhances the heat transfer between sample and its surroundings (cell, calorimeter, etc.) because the HP DSC was set at constant temperature during P-scan tests. Thus the absolute value of calorimetric signal increases until complete melting of the sample (2 in Figs. 3 and 5) and then decreases back to the initial baseline (23 in Figs. 3 and 5) representing an inert or nonevent (melting) phase. Therefore, a pressure-dependent endothermic calorimetric peak can be obtained for each P-scan experiment (Fig. 6a). For the sample mass and the scan rate (0.3 MPa/min) used, the endothermic peak (heat ow) spanned over 35 1.4 (n = 3) and 27 1.1 MPa (n = 3) with the summit occurring at 126 2.3 (n = 3) and 205 1.6 MPa (n = 3) for P-scan at -10 and -20C, respectively. The peak at the lower temperature (-20C) occurred at a higher pressure and also had a lower summit value and a shorter bandwidth (Fig. 6a). This is because of the pressuredependent characteristics of ice Iwater phase change (Eq. 2) and latent heat as empirically determined by Bridgman (1912):
L = 333 - 0.399 P - 0.000388 P 2

(3)

where L is latent heat of waterice I (J/g) (Chourot et al. 1997). The shape and size of the P-scan endothermic (heat ow rate) peak depends on several factors, such as sample mass, P-scan rate, thermo-physical properties of the cell and pressure medium and so on. As in conventional DSC experiments, a higher scan rate (either T-scan or P-scan) yields a wider span of the peak. During a conventional DSC test, the sample span (usually very small and made of out of light weight aluminum) is the only barrier to the heat-transfer in the chamber between the heating medium and test/reference samples. A larger heat capacity or a lower thermal conductivity of test cells implies a lower heat transfer rate and therefore a longer duration to reach and

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(a)
0 20 40 60 80 100 50 100 150 Pressure (MPa) 200 250

Heat flow rate (mW/g)

10C

20C

(b)
300 Thawing latent heat (J/g) 250 200 150 100 50 0 50 100 150 Pressure (MPa)
FIG. 6. PRESSURE-SCAN (0.3 MPa/min) OF PURE ICE WITH CALORIMETRIC TEMPERATURE AT -10 AND -20C: (A) THAWING HEAT FLOW RATE AND (B) THAWING LATENT HEAT

10C

20C

200

250

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pass the peak, thus resulting in a wide peak span. Attributed to higher pressures associated with HP DSC, the cell system itself is large and constructed of more sturdy material. The large heat capacity of the cell system strongly affects the span of the P-scan signal. Hence an appropriate calibration is vital for obtaining realistic data from these cells. When using a similar HP colorimeter with 1 g water and P-scan at 1 MPa/min, Le Bail et al. (2001) found the peak to span over 60 MPa. Randzio et al. (1994) reported a peak span of 70 MPa for solidliquid transition in benzene at a P-scan at 0.3 MPa/min. The peak span observed was smaller than these reported values because the sample mass was smaller and further a lower P-scan rate was used in this study. The onset and summit of the P-scan endothermic peak is related to the start and end of ice melting, respectively (Le Bail et al. 2002). A weightedaverage pressure ( P 1-2) was used to compare results from the P-scan tests with the reference diagram of Bridgman (1912), which was mathematically dened as:

P -2 1

P(q - q )dt = ( q - q ) dt
1 b t2 1 b

t2

(4)

where qb is the baseline of heat ow rate (mW); t is time (s); t1 and t2 are the time at peak onset and summit (s) (Fig. 5). The average pressure during ice melting was 119 2.2 (n = 3) and 200 1.6 MPa (n = 3) for P-scan at -10 and -20C, respectively (Table 1), as compared with the reference values of 112 1.4 and 195 1.0 MPa, respectively (Bridgman 1912) (Fig. 7). The area of endothermic heat ow rate peak represents the quantity of the heat transfer during the HP DSC test. The latent heat was evaluated by

TABLE 1. CHARACTERIZATION OF CALORIMETRIC SIGNAL PEAK (MEAN SD) FROM ISOTHERMAL PRESSURE-SCAN (0.3 MPa/min) EXPERIMENTS USING DISTILLED WATER Calorimetric temperature Pressure span of peak (MPa) Pressure at peak onset (P1, MPa) Reference phase-change pressure (MPa)* Average pressure ( P 1-2, MPa) Pressure at peak summit (P2, MPa) Measured latent heat (Lm, J/g) Calculated latent heat (L( P 1-2), J/g)* * Values were calculated using Eq. (2) or (3). -10 0.2C (n = 3) 34.8 1.4 111 1.8 112 1.4 119 2.2 126 2.3 278 1.0 280 1.1 -20 0.2C (n = 3) 25.9 1.1 194 1.5 195 1.0 200 1.6 205 1.6 233 1.9 237 1.4

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5 0 Temperature (C) 5 10 15 20 25
0.1

Average ( P12 ) Peak summit (melting end)

Water Reference diagram Ice-I

50 100 150 200 250

Pressure (MPa)
FIG. 7. PHASE TRANSITION BETWEEN PURE WATER AND ICE I OBSERVED DURING PRESSURE-SCAN TESTS AS COMPARED TO THE REFERENCE DIAGRAM (BRIDGMAN 1912)

integrating the calorimetric peak calibrated with the conversion ratio (Eq. 1) and subtracting the baseline:
Lm = 1 ( q - q b ) dt 1000 m

(5)

where Lm is measured latent heat of waterice I (J/g); m is water mass (g). Figure 6b shows the accumulation of thawing latent heat during the P-scan of test using pure water sample (ice). The top value of each curve in Fig. 6b indicates the total amount of absorbed or the latent heat released by the test sample, which was 278 1.0 (n = 3) and 233 1.9 J/g (n = 3) for P-scan at -10 and -20C, respectively. By substituting the average pressure ( P 1-2) into Eq. (3) (Bridgman 1912), the latent heat [L( P 1-2) = 333 - 0.399 P 1-2 0.000388 P 1-2] as 280 1.1 and 237 1.4 J/g for P-scan at -10 and -20C, respectively, was obtained (Table 1). For all P-scan tests combined, statistical analysis (t-test: paired two sample for means) indicated no signicant difference (P > 0.05, d.f. = 1/6) between experimentally evaluated latent heat (Lm) from this study and the calculated reference [L( P 1-2)] latent heat (Bridgman 1912). Based on the regression relationship between the values from the two

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400 Reference P-scan

Latent heat (J/g)

350

300 250

200 0 50 100 150 200 250 Pressure (MPa)

FIG. 8. MELTING LATENT HEAT OF PURE ICE MEASURED BY PRESSURE-SCAN (P-SCAN) TESTS AS COMPARE TO THE REFERENCE DATA (BRIDGMAN 1912)

methods, the following equation was obtained Lm = 0.987L( P 1-2) (R2 = 0.99, n = 6) for P-scan tests (Fig. 8). Isobaric T-scan Figure 9 is a typical calorimetric signal plot of a T-scan experiment (0.15C/min, 115 MPa, 0.5712 g ice). Figure 10 shows two peaks of heat ow rate against temperature during T-scan at atmospheric conditions (0.1 MPa) and at 115 MPa, respectively. Table 2 summarizes the results from isobaric Tscan tests. The endothermic peak at the higher pressure occurred at a lower temperature with a smaller peak area (Fig. 10a) because of the pressure related thermo-properties of water. The peak-onset temperature was -0.2 0.2 and -10.5 0.3C (n = 3) at 0.1 and 115 MPa, respectively (Table 2), as compared with calculated phase-change temperatures of 0 0.0 and -10.4 0.1C by Eq. (2), which correspond very well. Compared with isothermal P-scan peak, T-scan peak appeared larger in signal value because ice-melting duration in T-scan (Fig. 9) was shorter than that in P-scan (Fig. 5). However, T-scan rate (0.15C/min) in this study was quite small as compared with that used in conventional DSC test with very tiny sample (usually 1030 mg). HP DSC requires pressure resistant cells to

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Heat flow signal

Heat flow signal (mV) 0 0

Temperature

10

3 0 20 40 60 Time (min) 80 100 120

15

FIG. 9. A TYPICAL MEASUREMENT OF ISOBARIC TEMPERATURE-SCAN (0.15C/min) OF PURE ICE (0.5712 g) AT 115 MPa

TABLE 2. CHARACTERIZATION OF CALORIMETRIC SIGNAL PEAK (MEAN SD) FROM ISOBARIC TEMPERATURE-SCAN (0.15C/min) EXPERIMENTS USING DISTILLED WATER Calorimeter pressure Temperature at peak onset (C) Phase-change temperature (C)* Temperature at peak summit (C) Temperature span of peak (C) Measured latent heat (J/g) Calculated latent heat (J/g)* 0.1 0.0 MPa (n = 3) -0.2 0.2 0 0.0 3.8 0.3 10.2 0.5 318 2.1 333 0.0 115 0.9 MPa (n = 3) -10.5 0.3 -10.4 0.1 -6.8 0.3 9.8 0.4 277 2.4 282 0.5

* Values were calculated using Eq. (2) or (3).

hold sample. Thus sample size should be large enough to reduce the ratio of noise to HP calorimetric signal (Le Bail et al. 2001). A large sample can strengthen the signal, but tend to increase the span of the peak. Because of the large mass of the HP cell and sample, a low T-scan rate was selected to obtain a peak span as narrow as possible. The peak span was 10.2 0.5 (n = 3) and 9.8 0.4C (n = 3), showing peek summit at 3.8 0.3 and -6.8 0.3C, for T-scan (0.15C/min) of the ice sample at 0.1 and 115 MPa, respectively (Table 2). Although a low T-scan rate was used, the peak was much delayed

Calorimetric temperature (C)

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(a)
50 0 50 100 150

Heat flow rate (mW/g)

115 MPa
200 15 10 5 0 5

0.1 MPa
10 15 20

Temperature (C)

(b)
350 Thawing latent heat (J/g) 300 250 200 150 100 50 0 15 10 5 0 5 10 15 20 Temperature (C)
FIG. 10. TEMPERATURE SCAN (0.15C/min) OF PURE ICE AT 0.1 AND 115 MPa: (a) thawing heat flow rate and (b) thawing latent heat

115 MPa

0.1 MPa

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because of the large heat quantity required to keep temperature increase in sample and reference cells. The phase transition of water couldnt be well demonstrated during T-scan test under current experimental conditions. The latent heat was estimated using a similar integrating method to the P-scan peak analysis. The value was 318 2.1 and 277 2.4 J/g for T-scan at 0.1 and 115 MPa, respectively (Fig. 10b). Mathematically, the relationship between measured (Lm) and reference latent heat (L) was expressed as Lm = 0.961L (R2 = 0.95, n = 6). Although the regression agreement was good, and the values seem to be pretty close to each other, statistical analysis (t-test: paired two sample for means) demonstrated that measured value was signicantly (P < 0.05, d.f. = 1/6) lower than reference value of Bridgman (1912): 318 versus 333 and 277 versus 282 J/g, at atmospheric and HP conditions, respectively. T-scan test generally showed results that are slightly less accurate than P-scan probably attributed to inuence of large heat capacity of the mass of the cell and pressure medium during T-scan (temperature increase). While in P-scan test, the HP DSC worked at constant temperature. Overall the difference between the values from the two methods and those published in some classical literature was within a 10% error margin. CONCLUSIONS A HP DSC was examined for the evaluation of HP phase-transition behavior of pure water (in the melting mode). Two techniques (T-scan and Pscan) were used. Results obtained were statistical differences between the techniques as well as between the experimental and some published models. The pressure induced phase transition of ice Iwater was well pictured by Pscan. The latent heat of ice melting obtained by isothermal P-scan showed no signicant difference (P > 0.05) from reference data. This good agreement validated the reliability and accuracy of the HP DSC system during the isothermal P-scan test. HP calorimetry requires large cell mass to resist pressure, which could reduce the accuracy/efciency of calorimetric signal during isobaric T-scan test. T-scan tests produced good and consistent results but were slightly less accurate than P-scan counterparts or published models. The results obtained showed that the system could be successfully used for gathering HP phase-transition information, which is essential for the better understanding of pressure-dependent phase transition during HP freezing/thawing of foods. ACKNOWLEDGMENTS This study was partially funded by the European Project of Safe Ice (QLK1-CT-2002-02230) and the Strategic Grants Program of the Natural

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Sciences and Engineering Research Council of Canada. Experiments were carried out at ENITIAA, Nantes, France and analyses were performed at McGill. The authors wish to thank L. Guihard and J. Laurenceau for their technical support.

REFERENCES BRIDGMAN, P.W. 1912. Water in the liquid and ve solid forms under pressure. P. Am. Acad. Arts Sci. 47(13), 441558. BRIDGMAN, P.W. 1970. P-V-T relations in uids. In The Physics of the Pressure, (P.W. Bridgman, ed.) pp. 98148, Dover Publications, New York. CHEFTEL, J.C., LEVY, J. and DUMAY, E. 2000. Pressure-assisted freezing and thawing: Principles and potential applications. Food Rev. Int. 16(4), 453483. CHOUROT, J.M., BOILLEREAUX, L., HAVET, M. and LE BAIL, A. 1997. Numerical modeling of high pressure thawing: application to water thawing. J. Food Eng. 34, 6375. CHOUROT, J.M., LEBAIL, A. and CHEVALIER, D. 2000. Phase diagram of aqueous solution at high pressure and low temperature. High Pressure Res. 19(16), 191199. FUCHS, A.H., PRUZAN, P. and TERMINASSIAN, L. 1979. Thermal expansion of benzene at high pressure determined by a calorimetric method, its behavior near melting. J. Phys. Chem. Solids 40, 369374. GROLIER, J.P.E. and RANDZIO, S.L. 1997. Pressure effects on the thermodynamic properties of (n-hexane plus 1-hexanol) binary mixtures. Fluid Phase Equilibr. 133, 3544. HOGENBOOM, D.L., KARGEL, J.S., GANASAN, J.P. and LEE, L. 1995. Magnesium sulfate-water to 400 MPa using a novel piezometer: Densities, phase equilibria and planetological implications. Icarus 115, 258 277. KNORR, D. 1999. Process assessment of high-pressure processing of foods: An overview. In Processing Foods: Quality Optimization and Process Assessment, (F.A.R. Oliveira and J.C. Oliveira, eds.) pp. 249267, CRC Press, Boca Raton. LE BAIL, A., CHEVALIER, D. and CHOUROT, J.M. 2002. High pressure calorimetry: Application to phase change under pressure. In Trends in High Pressure Bioscience and Biotechnology, (R. Hayashi, ed.) pp. 607 613, Elsevier Science, Amsterdam. LE BAIL, A., CHEVALIER, D., CHOUROT, J.M. and MONTEAU, J.Y. 2001. High pressure calorimetry: Comparison of two systems

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