Thermochimica Acta 522 (2011) 9699

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Thermochimica Acta
journal homepage: www.elsevier.com/locate/tca

Enthalpy calibration for wide DSC peaks

Elena Moukhina
NETZSCH Geraetebau GmbH, BU Analyzing & Testing, Wittelsbacherstr. 42, Selb, Germany

a r t i c l e

i n f o

a b s t r a c t
The enthalpy calibration coefcient of a heat ux DSC instrument is temperature-dependent and therefore does not maintain a constant value across the entire temperature range of the measured DSC peak. Standard calibration procedures do not take into account any changes in this calibration coefcient during the melting peak of calibration materials. This produces a systematic error in enthalpy calibration, and in the further enthalpy evaluations of unknown materials. This systematic error is high for wide calibration peaks, measured with high heating rates and ceramic crucibles, and can be detected by heat ux DSC instruments. The current work estimates the value of this error and proposes an improvement to the enthalpy calibration procedure by using a DSC weighted mean temperature. 2011 Elsevier B.V. All rights reserved.

Article history: Available online 29 December 2010 Keywords: DSC enthalpy calibration DSC sensitivity

1. Introduction The temperature registered by heat ux DSC instruments is not measured directly at the sample. This registered temperature is therefore not exactly equal to the actual sample temperature. This fact has an inuence on the peak width. The closer the measured temperature is to the sample temperature, the narrower the peak and the steeper its left slope. But the peak width is never equal to zero, because the instrument has non-zero time constant. The temperature-dependent enthalpy calibration coefcient value does not stay constant across the entire temperature range of a measured DSC peak. An illustration of the temperature dependence of the enthalpy calibration coefcient is shown in Fig. 1. The measurements have been carried out on a NETZSCH DSC 404 F1 instrument for the melting of two metals with a large difference between their melting temperatures. Measurement conditions: 10 K/min, N2 atmosphere, 23 mg indium and 19.57 mg palladium. The original non-calibrated signals are shown in Fig. 1a. They have visually comparable areas with the ratio between them equal to 1.2. After enthalpy calibration, the same peaks have very different heights (Fig. 1b), and now the area of the palladium peak is 4.5 times higher than the area of the indium peak. Such a situation occurs because instrument sensitivity decreases with increasing temperature. Here it decreases by a factor of 3.8 with an average decrease rate of 0.56%/K. The reason for such a decrease is the more intensive heat exchange at high temperatures due to the higher inuences of the thermal conductivity of the gas and heat radiation [5].

Sometimes the samples cannot be directly measured in metal crucibles for chemical reasons. In such cases ceramic crucibles with lower heat conductivity are used. Of course, the enthalpy calibration must then also be done in ceramic crucibles. For these crucibles with low thermal conductivity, the instrument time constant is high and the measured calibration peaks are very wide. For a wide peak the temperature dependency of the enthalpy calibration coefcient may not be neglected. For example, the decreasing rate of the sensitivity coefcient, which is inverse to the enthalpy calibration coefcient, for an STA 449C is about 0.12%/K at temperatures below 300 C (Fig. 2). This means that for peaks with a width of 5.6 K the sensitivity change during the peak is 0.7%, and for a wide peak with a width of 48 K it changes by 5.7% (Fig. 3). The corresponding calibration error can be detected by precise DSC instruments. The enthalpy value of the calibration peak has a systematic deviation from the literature enthalpy value of melting. Finally this calibration results in a systematic error in enthalpy evaluations for all unknown materials, which are carried out using this erroneous enthalpy calibration. 2. Standard approach According to the standards ASTM E 0968-99 [1], DIN 51007 [2] and ISO 11357-1 [3] the enthalpy calibration coefcient is estimated as the ratio of the measured area to the literature value of the melting enthalpy. Thus the enthalpy calibration coefcient E at the melting temperature Tm is calculated by the expression: E(Tm ) = Hlit A (1)

Tel.: +49 9287 881 129; fax: +49 9287 881 144. E-mail address: elena.moukhina@netzsch.com 0040-6031/$ see front matter 2011 Elsevier B.V. All rights reserved. doi:10.1016/j.tca.2010.12.016

where Hlit is the literature value of melting enthalpy for calibration standard material, units [J/g]; E is the enthalpy calibration

E. Moukhina / Thermochimica Acta 522 (2011) 9699

DSC /V exo Indium,23mg Palladium, 19.57mg 1552C Area: 637.8 Vs

97

DSC /(V/mg)

exo
10 8 6 4
156.6C Area: 520.3 Vs

DSC 204F1, 10K/min, Al crucibles Area: 100.5 Vs/mg peak range: 156.4C...162.0C

15

10

5 STA 449, 20K/min, Al2O3 crucibles

2
0 6
DSC /mW exo Palladium, 19.57mg

Area: 22.69 Vs/mg peak range: 155C...203.3C

10

12

14

16

18

0 150 160 170 180 190 200 210

Time /min

Temperature /C
Fig. 3. Temperature range for area evaluation of 11 mg In depends on the measurement condition: crucible type and heating rate. Here it changes from 5.6 K to 48.3 K.

80

1552C Area: 3059 mJ

60

40
Indium,23mg

and the enthalpy calibration coefcient can be calculated using following expression:
156.6C Area: 677.6 mJ

20

E(Tm ) =

Tend Tstart

Hlit f (T )dT

(3)

0 6 8 10 12 14 16 18

Time /min
Fig. 1. (a) Non-calibrated melting peaks of Indium and palladium, measured by DSC 404 F1. Ratio of peak areas is 1.2. (b) Calibrated melting peaks of Indium and palladium, measured by DSC 404 F1. Ratio of peak areas is 4.5.

coefcient, units [mW/ V]; and A is the peak area determined for the measured non-calibrated peak, units [ V s/mg], calculated as
tend

A=
tstart

f (t)dt

(2)

f(t) is the measured DSC signal per mass unit, baseline is already subtracted, units [ V/mg]. Usually during calibration the heat ux DSC instrument runs under linear heating T = T0 + t with initial temperature T0 and heating rate . The temperature is registered not directly at the sample. If the design of the DSC instrument allows the registered temperature to be maintained equal to the programmed temperature (like NETZSCH DSC where temperature is registered at the bottom of the reference crucible), then = constant. In this case the area can be rewritten using an integration over temperature such as f(T)dT/,

This value is used as the enthalpy coefcient at the melting temperature, equal to the extrapolated onset temperature for the melting peak. According to the standards [1] and [3] the enthalpy calibration coefcient for different calibration materials must be found. These enthalpy calibration values are then interpreted as calibration coefcient values at the transition temperatures [4]. The temperature-dependent function is then created and used for evaluation of the enthalpy of unknown substances. This standard approach with different enthalpy calibration values at the transition temperatures is correct only for very sharp peaks, where the calibration coefcient has almost no changes across the entire peak temperature range. If the enthalpy calibration coefcient does change within the peak temperature range, then this standard procedure produces a systematic error. Let us estimate this error. 3. Problem with standard approach The melting peak of a calibration substance may be very wide, for example when heating rates are high, or when samples and crucibles have a high heat capacity or low thermal conductivity. Under such conditions the enthalpy calibration coefcient value does not stay constant across the entire peak temperature range. In this case, in a linear approximation, the enthalpy calibration coefcient can be written as the line E(T ) = E(Tm ) + k(T Tm ) where k is the slope: k= dE(T ) dT (5) (4)

Let us calculate the enthalpy of the same calibration peak using this enthalpy calibration coefcient. Hcalc =
Fig. 2. Sensitivity curve for STA449, based on melting peaks of In, Sn, Zn, Al, Au and Pd.

Tend

E(T )f (T )dT =
Tstart

Hlit +

Tend

f (T ) (T Tm )dT
Tstart

(6)

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E. Moukhina / Thermochimica Acta 522 (2011) 9699

The enthalpy calculated for the calibration peak is not equal to the literature value used for this peak during enthalpy calibration. The calculated enthalpy of the calibration peak would be equal to the literature value only if the enthalpy calibration coefcient value were to remain constant, with k = 0. But in reality the enthalpy calibration coefcient is a temperature-dependent function, and the second term in formula (6) is non-zero; this results in a systematic error in the calculated enthalpy value, which is found using the calibration coefcient from the standard calibration method. 4. Advanced approach with linear approximation It is proposed to change the standard approach by using the enthalpy calibration coefcient value not at the extrapolated onset temperature, but at another temperature Tnew to minimize the calibration error. E(Tnew ) =
Tend Tstart

Hlit f (T )dT

(7)

Fig. 4. New temperature for enthalpy calibration. For wide peak the DSC-weighted mean temperature is by 10 K higher than the transition temperature.

The calculated enthalpy for the same calibration peak with linear approximation for the new temperature is similar to expression (6), but Tm in the second term is replaced by Tnew : Hcalc = Hlit + k
Tend

f (T ) (T Tnew )dT
Tstart

(8)

The unknown new temperature Tnew can be determined, based on statement that the calculated enthalpy value and the literature value for the calibration peak must be the same. This means that the second term in (8) must be equal to zero. k
Tend

f (T ) (T Tnew )dT = 0
Tstart

(9)

The new temperature can therefore be found as:

Tend

temperature dependence of the enthalpy calibration coefcient is reduced to zero. The measurement for testing was carried out on an STA449 F1 with heavy Al2 O3 crucibles of 158 mg and at 20 K/min in order to have a peak of a signicant width (Fig. 4). The temperature range of such a peak is 47 K and the temperature difference between Tm and Tnew can reach 10 C. The slope k of the enthalpy calibration curve for this instrument is 0.0015 mW/( V K) and the area is 22.75 V s/mg. The absolute error of the calibration by the standard method is 0.33 mJ/mg, and this is 1.2% of the literature value for the enthalpy of melting of indium 28.6 J/g. If the calibration is carried out according to the new calibration procedure using the temperature of the center of gravity, then the calculated enthalpy of the calibration peak is exactly equal to the literature value.

Tnew =

Tstart Tend

T f (T )dT f (T )dT

(10) 6. Conclusion 1. The standard enthalpy calibration does not take into account that the enthalpy calibration coefcient changes across the temperature range of the peak. 2. The standard enthalpy calibration produces a systematic error in the enthalpy calibration coefcient, equal to k(Tm Tnew ). 3. Using the standard enthalpy calibration produces a systematic error for the calculated enthalpy of wide peaks, which is about 1.2% (In) for ceramic crucible and can be detected by DSC instruments. 4. The advanced approach uses a new temperature which is mathematically equal to the center of gravity of the calibration peak instead of the extrapolated onset temperature. For this advanced approach the systematic error arising from the linear temperature dependence of the enthalpy calibration coefcient is reduced to zero.

Tstart

The new temperature in this formula is calculated as the DSC weighted mean temperature. Mathematically this value is equal to the temperature for the center of gravity of the melting peak. If the enthalpy calibration coefcient value is taken at this new temperature, mathematically equal to the center of gravity of the calibration peak, then the second term in formula (8) is equal to zero and the calculated enthalpy of the calibration peak is exactly equal to the literature value of the melting enthalpy. 5. Systematic error in the enthalpy value achieved by the standard calibration procedure Substituting expressions (10) and (2) to Eq. (6) yields the following expression for the calculated enthalpy of the calibration peak with calibration by the standard procedure: Hcalc = Hlit + kA(Tm Tnew ) (11)

where the second term kA(Tm Tnew ) is an absolute error of the enthalpy for the calibration peak, when the enthalpy calibration is carried out using the standard procedure. If this second term is divided by area A, then the resulting value k(Tm Tnew ) has the meaning of the systematic error in the enthalpy calibration coefcient. Thus, if the enthalpy calibration coefcient value is assigned not to the transition temperature, but to the temperature of the peak center of gravity, then the systematic error arising from the linear

Acknowledgements The author wishes to express her thanks for valuable discussions to Erwin Kaisersberger, Netzsch-Geraetebau GmbH, Selb, Bavaria, Germany

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References
[1] ASTM E 0968-99, Standard Practice for Heat Flow Calibration of differential scanning calorimeters. [2] DIN 51007 Thermische Analyse, Differenzthermoanalyse (DTA), Grundlagen.

[3] ISO 11357-1:1998, Plastics-Differential Scanning Calorimetry (DSC) Part1: General Principles. [4] E. Gmelin, St.M. Sarge, Calibration of differential scanning calorimeters, Pure Appl. Chem. 67 (11) (1995) 17891800. [5] E. Moukhina, E. Kaisersberger, Thermochim. Acta 492 (2009) 101109.